Ethylene Oligomerization Processes

ABSTRACT

A process comprising A) continuously introducing into a reaction zone i) ethylene, ii) an iron salt, iii) a pyridine bisimine, iv) an organoaluminum compound, and v) an organic reaction medium, and B) forming an oligomer product in the reaction zone, the reaction zone having i) an iron of the iron salt concentration in a range of 5×10 −4  mmol/kg to 5×10 −3  mmol/kg, ii) an aluminum of the organoaluminum compound to iron of the iron salt molar ratio in a range of 300:1 to 800:1, ii) an ethylene partial pressure in a range of 750 psig to 1200 psig, iv) an ethylene to organic reaction medium mass ratio in a range of 0.8 to 4.5, v) a temperature in a range of 75° C. to 95° C., and optionally vi) a hydrogen partial pressure of at least 5 psi.

CROSS-REFERENCE TO RELATED APPLICATIONS

Not applicable.

FIELD

The present disclosure relates to processes for producing alpha olefins.More particularly, the present disclosure relates to improved processesfor oligomerizing ethylene.

BACKGROUND

Alpha olefins are important items of commerce. Their many applicationsinclude employment as intermediates in the manufacture of detergents, asprecursors to more environmentally friendly refined oils, as monomers,and as precursors for many other types of products. One method of makingalpha olefins is via oligomerization of ethylene in a catalytic reactioninvolving various types of catalysts and/or catalyst systems. Examplesof catalysts and catalyst systems used commercially to produce alphaolefins include alkylaluminum compounds, certain nickel-phosphinecomplexes, titanium halides with a Lewis acid (e.g., diethyl aluminumchloride), zirconium halides and/or zirconium alkoxides withalkylaluminum compounds. Additionally, there is a selective ethylenetrimerization and/or tetramerization catalyst system for producing1-hexene that uses a chromium containing compound (e.g., a chromiumcarboxylate), a nitrogen-containing ligand (e.g., a pyrrole), and ametal alkyl (e.g., alkyl aluminum compounds).

Several non-commercial oligomerization catalyst systems to produce alphaolefins are based upon metal complexes of pyridine bisimines, metalcomplexes of α-diimine compounds having a metal complexing group, andselective trimerization and/or tetramerization catalyst systems using ametal compound (e.g., a chromium compound) complex of adiphosphinylamine, phosphinyl formamidine, phosphinyl amidine, orphosphinyl guanidine. These catalyst systems typically use anorganoaluminum compound (e.g., aluminoxane) as a component of thecatalyst systems for olefin oligomerization.

Applications and demand for olefins (e.g., alpha olefins) continue tomultiply, and competition to supply them correspondingly intensifies.Thus, additional novel and improved catalyst systems and processes forolefin oligomerization are desirable.

SUMMARY

Disclosed herein is a process comprising A) continuously introducinginto a reaction zone i) ethylene, ii) an iron salt, iii) a pyridinebisimine, iv) an organoaluminum compound, and v) an organic reactionmedium, and B) forming an oligomer product in the reaction zone, thereaction zone having i) an iron of the iron salt concentration in arange of 5×10⁻⁴ mmol/kg to 5×10⁻³ mmol/kg, ii) an aluminum of theorganoaluminum compound to iron of the iron salt molar ratio in a rangeof 300:1 to 800:1, iii) an ethylene partial pressure in a range of 750psig to 1200 psig, iv) an ethylene to organic reaction medium mass ratioin a range of 0.8 to 4.5, v) a temperature in a range of 75° C. to 95°C., and optionally vi) a hydrogen partial pressure of at least 5 psi.

Also disclosed herein is a process comprising A) continuouslyintroducing into a reaction zone i) ethylene, ii) an pyridine bisimineiron salt complex, iii) an organoaluminum compound, and iv) an organicreaction medium; and B) forming an oligomer product in the reactionzone, the reaction zone having i) an iron of the pyridine bisimine ironsalt complex concentration in a range of 5×10⁻⁴ mmol/kg to 5×10⁻³mmol/kg, ii) an aluminum of the organoaluminum compound to iron of thepyridine bisimine iron salt complex molar ratio in a range of 300:1 to800:1, iii) an ethylene partial pressure in a range of 750 psig to 1200psig, iv) an ethylene to organic reaction medium mass ratio of 0.8 to4.5, and v) an average temperature in a range of 75° C. to 95° C.; andoptionally vi) a hydrogen partial pressure of at least 5 psi.

Also disclosed herein is a process comprising A) continuouslyintroducing into a reaction zone i) ethylene, ii) an iron salt iii) apyridine bisimine, iv) an organoaluminum compound, and v) an organicreaction medium comprising one or more C₈ to C₁₈ aliphatic hydrocarbons;and B) forming an oligomer product in the reaction zone, the reactionzone having an average temperature in a range of 75° C. to 95° C.

Also disclosed herein is a process comprising A) continuouslyintroducing into a reaction zone i) ethylene, ii) a pyridine bisimineiron salt complex, iii) an organoaluminum compound, and iv) an organicreaction medium comprising one or more C₈ to C₁₈ aliphatic hydrocarbons;and B) forming an oligomer product in the reaction zone, the reactionzone having an average temperature in a range of 75° C. to 95° C.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is and illustration of the oligomerization reaction systemutilized in the examples.

DETAILED DESCRIPTION

To define more clearly the terms used herein, the following definitionsare provided. Unless otherwise indicated, the following definitions areapplicable to this disclosure. If a term is used in this disclosure butis not specifically defined herein, the definition from the IUPACCompendium of Chemical Terminology, 2nd Ed (1997) can be applied, aslong as that definition does not conflict with any other disclosure ordefinition applied herein, or render indefinite or non-enabled any claimto which that definition is applied. To the extent that any definitionor usage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

Groups of elements of the periodic table are indicated using thenumbering scheme indicated in the version of the periodic table ofelements published in Chemical and Engineering News, 63(5), 27, 1985. Insome instances a group of elements can be indicated using a common nameassigned to the group; for example alkali metals for Group 1 elements,alkaline earth metals for Group 2 elements, transition metals for Group3-12 elements, and halogens for Group 17 elements.

Regarding claim transitional terms or phrases, the transitional term“comprising”, which is synonymous with “including,” “containing,”“having,” or “characterized by,” is inclusive or open-ended and does notexclude additional, unrecited elements or method steps. The transitionalphrase “consisting of” excludes any element, step, or ingredient notspecified in the claim. The transitional phrase “consisting essentiallyof” limits the scope of a claim to the specified materials or steps andthose that do not materially affect the basic and novelcharacteristic(s) of the claimed invention. A “consisting essentiallyof” claim occupies a middle ground between closed claims that arewritten in a “consisting of” format and fully open claims that aredrafted in a “comprising” format. Absent an indication to the contrary,when describing a compound or composition “consisting essentially of” isnot to be construed as “comprising,” but is intended to describe therecited component that includes materials which do not significantlyalter the composition or method to which the term is applied. Forexample, a feedstock consisting essentially of a material A can includeimpurities typically present in a commercially produced or commerciallyavailable sample of the recited compound or composition. When a claimincludes different features and/or feature classes (for example, amethod step, feedstock features, and/or product features, among otherpossibilities), the transitional terms comprising, consistingessentially of, and consisting of apply only to the feature class whichis utilized and it is possible to have different transitional terms orphrases utilized with different features within a claim. For example, amethod can comprise several recited steps (and other non-recited steps)but utilize a catalyst system preparation consisting of specific oralternatively, consist of specific steps and/or utilize a catalystsystem comprising recited components and other non-recited components.In another instance, the disclosure using a specified material of a canbe interpreted as comprising (consisting essentially of, or consistingof) at least one of the specified material, or can be interpreted ascomprising (consisting essentially of, or consisting of) one of more ofthe specified materials. For example, in general, a claim featurereciting “consisting essentially of a C₆ to C₁₆ compound” can beinterpreted or rewritten to recite “consisting essentially of at leastone C₆ to C₁₆ compound,” or “consisting essentially of one or more C₆ toC₁₆ compounds.”

While compositions and methods are described in terms of “comprising”various components or steps, the compositions and methods can also“consist essentially of” or “consist of” the various components orsteps.

In the specification and claims, the terms “a,” “an,” and “the” areintended, unless specifically indicated otherwise, to include pluralalternatives, e.g., at least one, or one or more. For instance, thedisclosure of “a trialkylaluminum compound” is meant to encompass onetrialkylaluminum compound, or mixtures or combinations of more than onetrialkylaluminum compound unless otherwise specified. In anotherinstance, the disclosure using a specified material can be interpretedas comprising (consisting essentially of, or consisting of) at least oneof the specified material, or can be interpreted as comprising(consisting essentially of, or consisting of) one of more of thespecified materials. For example, in general, a claim feature reciting“consisting essentially of a C₆ to C₁₆ compound” can be interpreted orrewritten to recite “consisting essentially of at least one C₆ to C₁₆compound,” or “consisting essentially of one or more C₆ to C₁₆compounds.”

In this disclosure, the terms first, second, and third, among others,can be utilized to differentiate multiple occurrences of a similarelement. For example a method can utilize two or more solvents indifferent steps of a method, or alternatively, two different solvents ina mixture. The differentiating term can be applied to any elementdescribed herein when necessary to provide a differentiation. It shouldbe understood that the numerical or alphabetical precedence of thedifferentiating terms do not imply a particular order or preference ofthe element in a method or compound described herein unless specificallyspecified otherwise.

In this disclosure, a process can have multiple steps or can includefeatures having a number of different elements (e.g., components in acatalyst system or components in an olefin oligomerization process,among other features). These steps and/or elements can be designatedutilizing the series a), b), c), etc., i), ii), iii), etc., (a), (b),(c), etc., and/or (i), (ii), (iii), etc. (among other designationseries) as necessary to provide a designation for each process stepand/or element. It should be understood that the numerical oralphabetical precedence of the designations within a designation seriesdoes not imply a particular order or preference of the process step in aprocess described herein, the feature(s) described herein, and/or anelement(s) in a feature unless specifically specified otherwise ornecessitated by other process steps, elements, and/or element features.Additionally, these designations series are provided to differentiatedifferent process steps and/or elements in a feature and can be utilizedas necessary, and without regard to the designation series utilized fora particular step, element, or feature utilized within this descriptionas long as the designation series consistently distinguish differentfeatures, different process steps, and/or different elements of afeature.

For any particular compound disclosed herein, the general structure orname presented is also intended to encompass all structural isomers,conformational isomers, and stereoisomers that can arise from aparticular set of substituents, unless indicated otherwise. Thus, ageneral reference to a compound includes all structural isomers unlessexplicitly indicated otherwise; e.g., a general reference to pentaneincludes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane while ageneral reference to a butyl group includes an n-butyl group, asec-butyl group, an iso-butyl group, and a tert-butyl group.Additionally, the reference to a general structure or name encompassesall enantiomers, diastereomers, and other optical isomers whether inenantiomeric or racemic forms, as well as mixtures of stereoisomers, asthe context permits or requires. For any particular formula or name thatis presented, any general formula or name presented also encompasses allconformational isomers, regioisomers, and stereoisomers that can arisefrom a particular set of substituents. Thus, a general reference to acompound includes all structural isomers unless explicitly indicatedotherwise; e.g., a general reference to a C₆ hydrocarbon refers to allhydrocarbon having 6 carbon atoms, a general reference to pentaneincludes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane, and ageneral reference to a butyl group includes an n-butyl group, asec-butyl group, an iso-butyl group, and a tert-butyl group.

A chemical “group” is described according to how that group is formallyderived from a reference or “parent” compound, for example, by thenumber of hydrogen atoms formally removed from the parent compound togenerate the group, even if that group is not literally synthesized inthis manner. These groups can be utilized as substituents or coordinatedor bonded to metal atoms. By way of example, an “alkyl group” formallycan be derived by removing one hydrogen atom from an alkane, while an“alkylene group” formally can be derived by removing two hydrogen atomsfrom an alkane. Moreover, a more general term can be used to encompass avariety of groups that formally are derived by removing any number (“oneor more”) hydrogen atoms from a parent compound, which in this examplecan be described as an “alkane group,” and which encompasses an “alkylgroup,” an “alkylene group,” and materials have three or more hydrogensatoms, as necessary for the situation, removed from the alkane.Throughout, the disclosure that a substituent, ligand, or other chemicalmoiety can constitute a particular “group” implies that the well-knownrules of chemical structure and bonding are followed when that group isemployed as described. When describing a group as being “derived by,”“derived from,” “formed by,” or “formed from,” such terms are used in aformal sense and are not intended to reflect any specific syntheticmethods or procedure, unless specified otherwise or the context requiresotherwise.

The term “substituted” when used to describe a group, for example, whenreferring to a substituted analog of a particular group, is intended todescribe any non-hydrogen moiety that formally replaces a hydrogen inthat group, and is intended to be non-limiting. A group or groups canalso be referred to herein as “unsubstituted” or by equivalent termssuch as “non-substituted,” which refers to the original group in which anon-hydrogen moiety does not replace a hydrogen within that group.“Substituted” is intended to be non-limiting and include inorganicsubstituents or organic substituents.

The term “organyl group” is used herein in accordance with thedefinition specified by IUPAC: an organic substituent group, regardlessof functional type, having one free valence at a carbon atom. Similarly,an “organylene group” refers to an organic group, regardless offunctional type, derived by removing two hydrogen atoms from an organiccompound, either two hydrogen atoms from one carbon atom or one hydrogenatom from each of two different carbon atoms. An “organic group” refersto a generalized group formed by removing one or more hydrogen atomsfrom carbon atoms of an organic compound. Thus, an “organyl group,” an“organylene group,” and an “organic group” can contain organicfunctional group(s) and/or atom(s) other than carbon and hydrogen, thatis, an organic group can comprise functional groups and/or atoms inaddition to carbon and hydrogen. For instance, non-limiting examples ofatoms other than carbon and hydrogen include halogens, oxygen, nitrogen,phosphorus, and the like. Non-limiting examples of functional groupsinclude ethers, aldehydes, ketones, esters, sulfides, amines,phosphines, and so forth.

For the purposes of this application, the term or variations of the term“organyl group consisting essentially of inert functional groups” refersto an organyl group (having a free valence on a carbon atom) wherein theorganic functional group(s) and/or atom(s) other than carbon andhydrogen present in the functional group are restricted to thosefunctional group(s) and/or atom(s) other than carbon and hydrogen whichdo not complex with a metal compound and/or are inert under the processconditions defined herein. Thus, the term or variation of the term“organyl group consisting essentially of inert functional groups”further defines the particular organyl groups that can be present withinthe organyl group consisting essentially of inert functional groups.Additionally, the term “organyl group consisting essentially of inertfunctional groups” can refer to the presence of one or more inertfunctional groups within the organyl group. The term or variation of theterm “organyl group consisting essentially of inert functional groups”definition includes the hydrocarbyl group as a member (among othergroups). Similarly, an “organylene group consisting essentially of inertfunctional groups” refers to an organic group formed by removing twohydrogen atoms from one or two carbon atoms of an organic compoundconsisting of inert functional groups and an “organic group consistingessentially of inert functional groups” refers to a generalized organicgroup consisting essentially of inert functional groups formed byremoving one or more hydrogen atoms from one or more carbon atoms of anorganic compound consisting of inert functional groups.

For purposes of this application, an “inert functional group” is a grouphaving a free valence on a heteroatom which does not substantiallyinterfere with the process described herein in which the material havingan inert functional group takes part and/or does not complex with themetal compound of the metal complex. The term “does not complex with themetal compound” can include groups that could complex with a metalcompound but in particular molecules described herein may not complexwith a metal compound due to its positional relationship within aligand. For example, while a hydrocarboxy group can complex with a metalcompound, a hydrocarboxy group located at a para position of asubstituted pyridine ring or substituted imine phenyl group can be aninert functional group because a single metal compound molecule cannotcomplex with the three nitrogen atoms of a pyridine bisimine ligand andthe para hydrocarboxy group within the same metal complex molecule.Thus, the inertness of a particular functional group is not only relatedto the functional group's inherent inability to complex the metalcompound but can also be related to the functional group's positionwithin the metal complex. Non-limiting examples of inert functionalgroups which do not substantially interfere with processes describedherein can include a halide (fluoride, chloride, bromide, and iodide),nitro, hydrocarboxy groups (e.g., alkoxy, and/or aroxy, among others),and/or hydrocarbosulfidyl groups (e.g., RS—), among others.

The term “hydrocarbon” whenever used in this specification and claimsrefers to a compound containing only carbon and hydrogen. Otheridentifiers can be utilized to indicate the presence of particulargroups in the hydrocarbon (e.g., halogenated hydrocarbon indicates thatthe presence of one or more halogen atoms replacing an equivalent numberof hydrogen atoms in the hydrocarbon). The term “hydrocarbyl group” isused herein in accordance with the definition specified by IUPAC: aunivalent group formed by removing a hydrogen atom from a hydrocarbon.Similarly, a “hydrocarbylene group” refers to a group formed by removingtwo hydrogen atoms from a hydrocarbon, either two hydrogen atoms fromone carbon atom or one hydrogen atom from each of two different carbonatoms. Therefore, in accordance with the terminology used herein, a“hydrocarbon group” refers to a generalized group formed by removing oneor more hydrogen atoms (as necessary for the particular group) from ahydrocarbon. A “hydrocarbyl group,” “hydrocarbylene group,” and“hydrocarbon group” can be acyclic or cyclic groups, and/or can belinear or branched. A “hydrocarbyl group,” “hydrocarbylene group,” and“hydrocarbon group” can include rings, ring systems, aromatic rings, andaromatic ring systems, which contain only carbon and hydrogen.“Hydrocarbyl groups,” “hydrocarbylene groups,” and “hydrocarbon groups”include, by way of example, aryl, arylene, arene, alkyl, alkylene,alkane, cycloalkyl, cycloalkylene, cycloalkane, aralkyl, aralkylene, andaralkane groups, among other groups, as members.

The term “alkane” whenever used in this specification and claims refersto a saturated hydrocarbon compound. Other identifiers can be utilizedto indicate the presence of particular groups in the alkane (e.g.,halogenated alkane indicates that the presence of one or more halogenatoms replacing an equivalent number of hydrogen atoms in the alkane).The term “alkyl group” is used herein in accordance with the definitionspecified by IUPAC: a univalent group formed by removing a hydrogen atomfrom an alkane. Similarly, an “alkylene group” refers to a group formedby removing two hydrogen atoms from an alkane (either two hydrogen atomsfrom one carbon atom or one hydrogen atom from two different carbonatoms). An “alkane group” is a general term that refers to a groupformed by removing one or more hydrogen atoms (as necessary for theparticular group) from an alkane. An “alkyl group,” “alkylene group,”and “alkane group” can be acyclic or cyclic groups, and/or can be linearor branched unless otherwise specified.

A cycloalkane is a saturated cyclic hydrocarbon, with or without sidechains, for example, cyclobutane. Unsaturated cyclic hydrocarbons havingone or more endocyclic double or one triple bond are called cycloalkenesand cycloalkynes, respectively. Cycloalkenes and cycloalkynes havingonly one, only two, only three, etc . . . endocyclic double or triplebonds, respectively, can be identified by use of the term “mono,” “di,”“tri, etc . . . within the name of the cycloalkene or cycloalkyne.Cycloalkenes and cycloalkynes can further identify the position of theendocyclic double or triple bonds.

A “cycloalkyl group” is a univalent group derived by removing a hydrogenatom from a ring carbon atom of a cycloalkane. For example, a1-methylcyclopropyl group and a 2-methylcyclopropyl group areillustrated as follows.

Similarly, a “cycloalkylene group” refers to a group derived by removingtwo hydrogen atoms from a cycloalkane, at least one of which is a ringcarbon. Thus, a “cycloalkylene group” includes both a group derived froma cycloalkane in which two hydrogen atoms are formally removed from thesame ring carbon, a group derived from a cycloalkane in which twohydrogen atoms are formally removed from two different ring carbons, anda group derived from a cycloalkane in which a first hydrogen atom isformally removed from a ring carbon and a second hydrogen atom isformally removed from a carbon atom that is not a ring carbon. A“cycloalkane group” refers to a generalized group formed by removing oneor more hydrogen atoms (as necessary for the particular group and atleast one of which is a ring carbon) from a cycloalkane. It should benoted that according to the definitions provided herein, generalcycloalkane groups (including cycloalkyl groups and cycloalkylenegroups) include those having zero, one, or more than one hydrocarbylsubstituent groups attached to a cycloalkane ring carbon atom (e.g., amethylcyclopropyl group) and is member of the group of hydrocarbongroups. However, when referring to a cycloalkane group having aspecified number of cycloalkane ring carbon atoms (e.g., cyclopentanegroup or cyclohexane group, among others), the base name of thecycloalkane group having a defined number of cycloalkane ring carbonatoms refers to the unsubstituted cycloalkane group (including having nohydrocarbyl groups located on cycloalkane group ring carbon atom).Consequently, a substituted cycloalkane group having a specified numberof ring carbon atoms (e.g., substituted cyclopentane or substitutedcyclohexane, among others) refers to the respective group having one ormore substituent groups (including halogens, hydrocarbyl groups, orhydrocarboxy groups, among other substituent groups) attached to acycloalkane group ring carbon atom. When the substituted cycloalkanegroup having a defined number of cycloalkane ring carbon atoms is amember of the group of hydrocarbon groups (or a member of the generalgroup of cycloalkane groups), each substituent of the substitutedcycloalkane group having a defined number of cycloalkane ring carbonatoms is limited to hydrocarbyl substituent group. One can readilydiscern and select general groups, specific groups, and/or individualsubstituted cycloalkane group(s) having a specific number of ringcarbons atoms which can be utilized as member of the hydrocarbon group(or a member of the general group of cycloalkane groups).

The term “olefin” whenever used in this specification and claims refersto hydrocarbon compounds that have at least one carbon-carbon doublebond that is not part of an aromatic ring or an aromatic ring system.The term “olefin” includes aliphatic and aromatic, cyclic and cyclic,and/or linear and branched compounds having at least one carbon-carbondouble bond that is not part of an aromatic ring or ring system unlessspecifically stated otherwise. Olefins having only one, only two, onlythree, etc . . . carbon-carbon double bonds can be identified by use ofthe term “mono,” “di,” “tri,” etc . . . within the name of the olefin.The olefins can be further identified by the position of thecarbon-carbon double bond(s).

The term “alkene” whenever used in this specification and claims refersa linear or branched aliphatic hydrocarbon olefin that has one or morecarbon-carbon double bonds. Alkenes having only one, only two, onlythree, etc . . . such multiple bond can be identified by use of the term“mono,” “di,” “tri,” etc. within the name. Alkenes can be furtheridentified by the position of the carbon-carbon double bond(s). Otheridentifiers can be utilized to indicate the presence or absence ofparticular groups within an alkene. For example, a haloalkene refers toan alkene having one or more hydrogen atoms replace with a halogen atom.

The term “alpha olefin” as used in this specification and claims refersto an olefin that has a carbon-carbon double bond between the first andsecond carbon atom of the longest contiguous chain of carbon atoms. Theterm “alpha olefin” includes linear and branched alpha olefins unlessexpressly stated otherwise. In the case of branched alpha olefins, abranch can be at the 2-position (a vinylidene) and/or the 3-position orhigher with respect to the olefin double bond. The term “vinylidene”whenever used in this specification and claims refers to an alpha olefinhaving a branch at the 2-position with respect to the olefin doublebond. By itself, the term “alpha olefin” does not indicate the presenceor absence of other carbon-carbon double bonds unless explicitlyindicated.

The term “normal alpha olefin” whenever used in this specification andclaims refers to a linear aliphatic mono-olefin having a carbon-carbondouble bond between the first and second carbon atoms. It is noted that“normal alpha olefin” is not synonymous with “linear alpha olefin” asthe term “linear alpha olefin” can include linear olefinic compoundshaving a double bond between the first and second carbon atoms andadditional double bonds.

An aliphatic compound is an acyclic or cyclic, saturated or unsaturated,carbon compound, excluding aromatic compounds. An “aliphatic group” is ageneralized group formed by removing one or more hydrogen atoms (asnecessary for the particular group) from the carbon atom of an aliphaticcompound. Aliphatic compounds and therefore aliphatic groups can containorganic functional group(s) and/or atom(s) other than carbon andhydrogen.

An aromatic compound is a compound containing a cyclically conjugateddouble bond system that follows the Hückel (4 n+2) rule and contains (4n+2) pi-electrons, where n is an integer from 1 to 5. Aromatic compoundsinclude “arenes” (hydrocarbon aromatic compounds) and “heteroarenes,”also termed “hetarenes” (heteroaromatic compounds formally derived fromarenes by replacement of one or more methine (—C═) carbon atoms of thecyclically conjugated double bond system with a trivalent or divalentheteroatoms, in such a way as to maintain the continuous pi-electronsystem characteristic of an aromatic system and a number of out-of-planepi-electrons corresponding to the Hückel rule (4 n+2). While arenecompounds and heteroarene compounds are mutually exclusive members ofthe group of aromatic compounds, a compound that has both an arene groupand a heteroarene group are generally considered a heteroarene compound.Aromatic compounds, arenes, and heteroarenes can be monocyclic (e.g.,benzene, toluene, furan, pyridine, methylpyridine) or polycyclic unlessotherwise specified. Polycyclic aromatic compounds, arenes, andheteroarenes, include, unless otherwise specified, compounds wherein thearomatic rings can be fused (e.g., naphthalene, benzofuran, and indole),compounds where the aromatic groups can be separate and joined by a bond(e.g., biphenyl or 4-phenylpyridine), or compounds where the aromaticgroups are joined by a group containing linking atoms (e.g., carbon—themethylene group in diphenylmethane; oxygen—diphenyl ether;nitrogen—triphenyl amine; among others linking groups). As disclosedherein, the term “substituted” can be used to describe an aromaticgroup, arene, or heteroarene wherein a non-hydrogen moiety formallyreplaces a hydrogen in the compound, and is intended to be non-limiting.

An “aromatic group” refers to a generalized group formed by removing oneor more hydrogen atoms (as necessary for the particular group and atleast one of which is an aromatic ring carbon atom) from an aromaticcompound. For a univalent “aromatic group,” the removed hydrogen atommust be from an aromatic ring carbon. For an “aromatic group” formed byremoving more than one hydrogen atom from an aromatic compound, at leastone hydrogen atom must be from an aromatic hydrocarbon ring carbon.Additionally, an “aromatic group” can have hydrogen atoms removed fromthe same ring of an aromatic ring or ring system (e.g., phen-1,4-ylene,pyridin-2,3-ylene, naphth-1,2-ylene, and benzofuran-2,3-ylene), hydrogenatoms removed from two different rings of a ring system (e.g.,naphth-1,8-ylene and benzofuran-2,7-ylene), or hydrogen atoms removedfrom two isolated aromatic rings or ring systems (e.g.,bis(phen-4-ylene)methane).

An arene is aromatic hydrocarbon, with or without side chains (e.g.,benzene, toluene, or xylene, among others). An “aryl group” is a groupderived from the formal removal of a hydrogen atom from an aromatic ringcarbon of an arene. It should be noted that the arene can contain asingle aromatic hydrocarbon ring (e.g., benzene, or toluene), containfused aromatic rings (e.g., naphthalene or anthracene), and contain oneor more isolated aromatic rings covalently linked via a bond (e.g.,biphenyl) or non-aromatic hydrocarbon group(s) (e.g., diphenylmethane).

Similarly, an “arylene group” refers to a group formed by removing twohydrogen atoms (at least one of which is from an aromatic ring carbon)from an arene. An “arene group” refers to a generalized group formed byremoving one or more hydrogen atoms (as necessary for the particulargroup and at least one of which is an aromatic ring carbon) from anarene. It should be noted that according the definitions providedherein, general arene groups (including an aryl group and an arylenegroup) include those having zero, one, or more than one hydrocarbylsubstituent groups located on an aromatic hydrocarbon ring or ringsystem carbon atom (e.g., a toluene group or a xylene group, amongothers) and is a member of the group of hydrocarbon groups. However, aphenyl group (or phenylene group) and/or a naphthyl group (ornaphthylene group) refer to the specific unsubstituted arene groups(including no hydrocarbyl group located on an aromatic hydrocarbon ringor ring system carbon atom). Consequently, a substituted phenyl group orsubstituted naphthyl group refers to the respective arene group havingone or more substituent groups (including halogens, hydrocarbyl groups,or hydrocarboxy groups, among others) located on an aromatic hydrocarbonring or ring system carbon atom. When the substituted phenyl groupand/or substituted naphtyl group is a member of the group of hydrocarbongroups (or a member of the general group of arene groups), eachsubstituent is limited to a hydrocarbyl substituent group. One havingordinary skill in the art can readily discern and select general phenyland/or naphthyl groups, specific phenyl and/or naphthyl groups, and/orindividual substituted phenyl or substituted naphthyl groups which canbe utilized as a member of the group of hydrocarbon groups (or a memberof the general group of arene groups).

An “aralkyl group” is an aryl-substituted alkyl group having a freevalance at a non-aromatic carbon atom (e.g., a benzyl group, or a2-phenyleth-1-yl group, among others). Similarly, an “aralkylene group”is an aryl-substituted alkylene group having two free valencies at asingle non-aromatic carbon atom or a free valence at two non-aromaticcarbon atoms while an “aralkane group” is a generalized aryl-substitutedalkane group having one or more free valencies at a non-aromatic carbonatom(s). It should be noted that according the definitions providedherein, general aralkane groups include those having zero, one, or morethan one hydrocarbyl substituent groups located on an aralkane aromatichydrocarbon ring or ring system carbon atom and is a member of the groupof hydrocarbon groups. However, specific aralkane groups specifying aparticular aryl group (e.g., the phenyl group in a benzyl group or a2-phenylethyl group, among others) refer to the specific unsubstitutedaralkane groups (including no hydrocarbyl group located on the aralkanearomatic hydrocarbon ring or ring system carbon atom). Consequently, asubstituted aralkane group specifying a particular aryl group refers toa respective aralkane group having one or more substituent groups(including halogens, hydrocarbyl groups, or hydrocarboxy groups, amongothers). When the substituted aralkane group specifying a particulararyl group is a member of the group of hydrocarbon groups (or a memberof the general group of aralkane groups), each substituent is limited toa hydrocarbyl substituent group. One can readily discern and selectsubstituted aralkane groups specifying a particular aryl group which canbe utilized as a member of the group of hydrocarbon groups (or a memberof the general group of aralkane groups).

A “primary carbon atom group,” a “secondary carbon atom group,” a“tertiary carbon atom group,” and a “quaternary carbon atom group”describe the type of carbon atom which would be created when the groupis attached to a base structure. A “primary carbon atom group” is agroup wherein the carbon atom bonded to the base structure is alsobonded to three monovalent atoms (e.g., hydrogen or halides) in additionto the base structure. A methyl group, a trifluormethyl group (amongother group) attached to a base structure represent potential “primarycarbon atom groups.” A “secondary carbon atom group” is a group whereinthe carbon atom bonded to the base structure is bonded to one othernon-monovalent atom (e.g., carbon, nitrogen, or oxygen, among others)and two monovalent atoms. An ethyl group, a 1-chloroeth-1-yl group, anda methoxymethyl group (among others) attached to a base structurerepresent potential “secondary carbon atom groups.” A “tertiary carbongroup” is a group wherein the carbon atom bonded to the base structureis bonded to two other non-monovalent atoms and one monovalent atom. Anisopropyl group, a 2-chloroprop-1-yl group, a phenyl group, and a1-methoxyethy-1-yl group (among others) attached to a base structurerepresent potential “tertiary carbon groups.” A “quaternary carbongroup” is a group wherein the carbon atom bonded to the base structureis also bonded to three other non-monovalent atoms. A tert-butyl groupand a 2-methoxyprop-2-yl group (among others) attached to a basestructure represent potential “quaternary carbon groups.”

A “halide” has its usual meaning; therefore, examples of halides includefluoride, chloride, bromide, and iodide.

Within this disclosure the normal rules of organic nomenclature willprevail. For instance, when referencing substituted compounds or groups,references to substitution patterns are taken to indicate that theindicated group(s) is (are) located at the indicated position and thatall other non-indicated positions are hydrogen. For example, referenceto a 4-substituted phenyl group indicates that there is a non-hydrogensubstituent located at the 4 position and hydrogens located at the 2, 3,5, and 6 positions. By way of another example, reference to a3-substituted naphth-2-yl indicates that there is a non-hydrogensubstituent located at the 3 position and hydrogens located at the 1, 4,5, 6, 7, and 8 positions. References to compounds or groups havingsubstitutions at positions in addition to the indicated position will bereference using comprising or some other alternative language. Forexample, a reference to a phenyl group comprising a substituent at the4-position refers to a group having a non-hydrogen atom at the4-position and hydrogen or any other non-hydrogen group at the 2-, 3-,5-, and 6-positions.

The term “reaction zone effluent,” and it derivatives (e.g.,oligomerization reaction zone effluent) generally refers to all thematerial which exits the reaction zone. The term “reaction zoneeffluent,” and its derivatives, can also be prefaced with otherdescriptors that limit the portion of the reaction zone effluent beingreferenced. For example, the term “reaction zone effluent” would referto all material exiting the reaction zone (e.g., product and solvent ordiluent, among others), while the term “olefin reaction zone effluent”refers to only the olefins within the reaction zone effluent and theterm “oligomer product reactor effluent” refers to oligomer productwithin the reaction zone effluent.

The term “oligomerization,” and its derivatives, refers to processeswhich produce a mixture of products containing at least 70 wt. %products containing from 2 to 30 monomer units. Similarly, an “oligomer”is a product that contains from 2 to 30 monomer units while an “oligomerproduct” or an “oligomerization product” includes all products made bythe “oligomerization” process including the “oligomers” and productswhich are not “oligomers” (e.g., products which contain more than 30monomer units). It should be noted that the monomer units in the“oligomer” or “oligomerization product” do not have to be the same. Forexample, an “oligomer,” “oligomer product,” or “oligomerization product”of an “oligomerization” process using ethylene and propylene as monomerscan contain both ethylene and/or propylene units.

“K value” (sometimes referred to as Schulz-Flory chain growth factor, Kor Schulz-Flory K value) can be defined the equation: K=X_(q+1)/X_(q)wherein X_(q+1) is the number of moles of oligomer product producedhaving q+1 monomer (e.g., ethylene) units and X_(q) is the number ofmoles of oligomer product produced having q monomer (e.g., ethylene)units. Generally, the K value can be determined using any two oligomersof the oligomer product which differs in the number of monomer unitsby 1. However, one would appreciate that product isolation and analysiscan lead to inaccuracies in a determined oligomer product distributionusing particular oligomers (e.g., incomplete recovery of gaseous productand/or solid product during product isolation). One having ordinaryskill in the art would recognize such issues and can choose theappropriate oligomers upon which to base the determination of theoligomer product distribution K value.

“Catalyst system productivity” is defined as grams of a product producedper gram (or mole) of metal in the catalyst system utilized in theoligomerization. Catalyst system activity is defined as grams of aproduct produced per gram (or mole) of metal per unit of time (e.g.,hour) of an oligomerization. Catalyst system productivity and/oractivity can be stated in terms of various products of anoligomerization and/or components of catalyst system. For example, in anethylene oligomerization process utilizing a catalyst system comprisingan iron salt complex and an organoaluminum compound, the catalyst systemproductivity which can be utilized include (g oligomer product)/(g Fe),among other productivities.

Unless otherwise specified, the terms contacted, combined, and “in thepresence of” refer to any addition sequence, order, or concentration forcontacting or combining the recited two or more components. Thecombining or contacting of the components, according to the variousmethods described herein can occur in one or more contact zones undersuitable contact conditions such as temperature, pressure, contact time,flow rates, etc. . . . The contact zone can be disposed in a vessel(e.g., a storage tank, tote, container, mixing vessel, reactor, etc.), alength of pipe (e.g., a tee, inlet, injection port, or header forcombining component feed lines into a common line), or any othersuitable apparatus for bringing the components into contact, unlessotherwise specified. The processes can be carried out in a batch orcontinuous process as is suitable for a given embodiment, unlessotherwise specified.

The terms “simultaneously,” “simultaneously contact,” “contactsimultaneously,” and their derivatives when referring to a contactmethod refers to a contact method wherein the two or more recitedcompounds, mixtures, streams, and/or compositions are contacted byflowing into a common junction, pot, vessel, or reactor, among others,at the same time. The terms “substantially simultaneously,”“substantially simultaneously contact,” “contact substantiallysimultaneously,” and their derivatives when referring to a contactmethod refers to a contact method wherein, during the contact of two ormore recited compounds, mixtures, streams, and/or compositions, the twoor more recited compounds, mixtures, streams, and/or compositions arecontacted such that for some period during the contact process the twoor more recited compounds, mixtures, streams, and/or compositions flowinto a common junction, pot, vessel, or reactor at the same time. Itshould be noted that the terms “substantially simultaneously,”“substantially simultaneously contact,” “contact substantiallysimultaneously,” and their derivatives do not mean that the two or morerecited compounds, mixtures, streams, and/or compositions are contactedsimultaneously over the entire addition of each of the two or morerecited compounds, mixtures, streams, and/or compositions. The terms“substantially simultaneously,” “substantially simultaneously contact,”“contact substantially simultaneously,” and it derivatives includescenarios where the flow of one of the (or less than all of the) recitedcompounds, mixtures, streams, and/or compositions can be initiated intothe common junction, pot, vessel, or reactor before the others and/orthe flow of one of the (or less than all of the) recited compounds,mixtures, streams, and/or compositions into the common junction, pot,vessel, or reactor can be completed, stopped, or discontinued before theother recited compounds, mixtures, streams, and/or compositions. In anyembodiment or aspect described herein, the terms “simultaneously,”“simultaneously contact,” “contact simultaneously,” and theirderivatives, these terms can be modified by the inclusion of a termproviding a quantity of the each of the recited compounds, mixtures,streams, and/or compositions which can be contacted simultaneouslyindicate scenarios of various degrees of “substantially simultaneously,”“substantially simultaneously contact,” “contact substantiallysimultaneously,” and their derivatives. For example, at least 20%, 30%,40%, 50%, 60%, 70%, 75%, 80%, 85%, 90%, 95% of each of the recitedcompounds, mixtures, streams, and/or compositions can be “simultaneouslycontacted” or “contacted simultaneously.” Generally, the percentages ofthe recited compounds, mixtures, streams, and/or compositions that canbe “simultaneously contacted” or “contacted simultaneously” can be byweight (wt. %), by volume (volume %), or by mole (mole %). Unlessotherwise specified, recited compounds, mixtures, streams, and/orcompositions that are “substantially simultaneously,” “substantiallysimultaneously contact,” “contact substantially simultaneously,” andtheir derivatives shall mean that at least 50% of each of the recitedcompounds, mixtures, streams, and/or compositions can be “simultaneouslycontacted” or “contacted simultaneously.”

It should be further noted, that in reference to contact method orprocess, “simultaneously,” “simultaneously contact,” “contactsimultaneously,” “substantially simultaneously contact,” “contactsubstantially simultaneously,” and their derivatives is different than aprocess or method wherein one or more a first materials (e.g., compound,mixture, stream, and/or composition) already resides in a pot, vessel,or reactor and one or more other compounds, mixtures, streams, and/orcompositions are added to the pot, vessel, or reactor. In this instancethe first material in the pot, vessel, or reactor does not flow into thepot, vessel, or reactor concurrently with the other compounds, mixtures,streams, and/or compositions and the material in the pot. Thus, thefirst material and the other compounds, mixtures, streams, and/orcompositions cannot be said to be “simultaneously contacted,” “contactedsimultaneously,” “substantially simultaneously contacted,” or “contactedsubstantially simultaneously” with the other component(s).

In an aspect, the processes disclosed herein can relate to processescomprising A) continuously introducing into a reaction zone i) ethylene,ii) a pyridine bisimine iron salt complex, iii) an organoaluminumcompound, and iv) an organic reaction medium; and B) forming an oligomerproduct in the reaction zone; or alternatively, comprising A)continuously introducing into a reaction zone i) ethylene, ii) an ironsalt, iii) a pyridine bisimine, iv) an organoaluminum compound, and v)an, at least one, or one or more, organic reaction medium(s); and B)forming an oligomer product in the reaction zone. Optionally, theprocesses can further comprise continuously introducing hydrogen intothe reaction zone. In embodiments utilizing hydrogen, the oligomerproduct can be formed at, the reaction zone can have, or the reactionzone can operate at a specified hydrogen partial pressure. In anembodiment, the processes can further comprise continuously discharginga reaction zone effluent from the reaction zone. In another embodiment,the processes can further comprise a) introducing the, the at least one,or the one or more, organic reaction mediums to the reaction zone priorto introducing the iron salt pyridine bisimine complex (or the iron saltand/or the pyridine bisimine compound) or the ethylene to the reactionzone and/or b) introducing 1) the pyridine bisimine iron salt complex(or alternatively the iron salt and the pyridine bisimine) to thereaction zone prior to introducing ethylene to the reaction zone. In anaspect, the oligomer product can be formed at, the reaction zone canhave, or the reaction zone can operate at conditions capable of formingan oligomer product. Generally, the pyridine bisimine iron salt complex,the pyridine bisimine, the iron salt, the organoaluminum compound, the,the at least one, or the one or more, organic reaction medium(s), thereaction zone, the conditions at which the oligomer product can beformed, the conditions which the reaction zone can have, and/or theconditions at which the reaction can operate, where applicable, areindependent elements of process described herein and are independentlydescribed herein. These independently described process elements can beutilized in any combination, and without limitation to further describedthe processes provided herein.

In one aspect, the process described herein can comprise A) continuouslyintroducing into a reaction zone i) ethylene, ii) a pyridine bisimineiron salt complex, iii) an organoaluminum compound, and iv) an organicreaction medium comprising, or consisting essentially of, a, at leastone, or one or more, specific organic reaction medium(s); and B) formingan oligomer product in the reaction zone, the reaction zone having aspecified average temperature; or alternatively, comprise i) ethylene,ii) an iron salt, iii) a pyridine bisimine, iv) an organoaluminumcompound, and v) an organic reaction medium comprising, or consistingessentially of, a at least one, or one or more, specific organicreaction medium(s); and B) forming an oligomer product in the reactionzone, the reaction zone having a specified average temperature. In anembodiment, the processes can further comprise continuously discharginga reaction zone effluent from the reaction zone. In another embodiment,the processes can further comprise a) introducing the, the at least one,or the one or more, organic reaction medium(s) to the reaction zoneprior to introducing the iron salt pyridine bisimine complex, the ironsalt, the pyridine bisimine compound, or ethylene to the reaction zoneand/or b) introducing 1) the pyridine bisimine iron salt complex (oralternatively the iron salt and the pyridine bisimine) to the reactionzone prior to introducing ethylene to the reaction zone. In anembodiment wherein an iron salt and a pyridine bisimine are continuouslyintroduced into a reaction zone, the oligomer product can be formed at,the reaction zone can have, or the reaction zone can operate at aspecified an iron salt to pyridine bisimine equivalent ratio. In anembodiment of these processes, the oligomer product can be formed at,the reaction zone can have, or the reaction zone can operate at aspecified iron of the pyridine bisimine iron salt complex concentration,a specified aluminum of the organo aluminum compound to iron of thepyridine bisimine iron salt complex molar ratio, a specified ethylenepartial pressure, a specified ethylene to organic reaction medium massratio, a specified average temperature, a specified aluminum of theorganoaluminum compound concentration, and/or a specified ethylene toorganic reaction medium mass ratio. In other embodiments, theseprocesses can optionally continuously introduce hydrogen into thereaction zone. In embodiments utilizing hydrogen, the oligomer productcan be formed at, the reaction zone can have, or the reaction zone canoperate at a specified hydrogen partial pressure. Generally, thepyridine bisimine iron salt complex, the pyridine bisimine, the ironsalt, the organoaluminum compound, the organic reaction medium, thereaction zone, the specified iron of the pyridine bisimine iron saltcomplex concentration, the specified aluminum of the organo aluminumcompound to iron of the pyridine bisimine iron salt complex molar ratio,the specified iron salt to pyridine bisimine equivalent ratio, thespecified ethylene partial pressure, the specified ethylene to organicreaction medium mass ratio, the specified average temperature, thespecified aluminum of the organoaluminum compound concentration, thespecified ethylene to organic reaction medium mass ratio, the specifiedhydrogen partial pressure, and the specified organic reaction medium,where applicable, are independent elements of process described hereinand are independently described herein. These independently describedprocess elements can be utilized in any combination, and withoutlimitation to further describe the processes provided herein.

In another aspect, the process described herein can comprise A)continuously introducing into a reaction zone i) ethylene, ii) apyridine bisimine iron salt complex, iii) an organoaluminum compound,and iv) an, at least one, or one or more, organic reaction medium(s);and B) forming an oligomer product in the reaction zone, where theoligomer product can be formed at, the reaction zone can have, or thereaction zone can operate at i) a specified iron of the pyridinebisimine iron salt complex concentration, ii) a specified aluminum ofthe organo aluminum compound to iron of the pyridine bisimine iron saltcomplex molar ratio, iii) a specified ethylene partial pressure, iv) aspecified ethylene to organic reaction medium mass ratio, and v) aspecified average temperature; or alternatively, comprising A)continuously introducing into a reaction zone i) ethylene, ii) an ironsalt, iii) a pyridine bisimine, iv) an organoaluminum compound, and v)an organic reaction medium comprising, or consisting essentially of, atleast one, or one or more, specific aliphatic hydrocarbon(s); and B)forming an oligomer product in the reaction zone, where the oligomerproduct can be formed at, the reaction zone can have, or the reactionzone can operate at i) a specified iron of the pyridine bisimine ironsalt complex concentration, ii) a specified aluminum of the organoaluminum compound to iron of the pyridine bisimine iron salt complexmolar ratio, iii) a specified ethylene partial pressure, iv) a specifiedethylene to organic reaction medium mass ratio, and v) a specifiedaverage temperature. In an embodiment, the processes can furthercomprise continuously discharging a reaction zone effluent from thereaction zone. In another embodiment, the processes can further comprisea) introducing the, at least one, or one or more, organic reactionmedium(s) to the reaction zone prior to introducing the iron saltpyridine bisimine complex, the iron salt, the pyridine bisiminecompound, or the ethylene to the reaction zone and/or b) introducing 1)the pyridine bisimine iron salt complex (or alternatively the iron saltand the pyridine bisimine) to the reaction zone prior to introducingethylene to the reaction zone. In an embodiment, these processes canutilize a, at least one, or one or more, specified organic reactionmedium(s). In other embodiments, these processes can operate such thatthe oligomer product can be formed at, the reaction zone can have, orthe reaction zone can operate at a specified aluminum of theorganoaluminum compound concentration, and/or a specified ethylene toorganic reaction medium mass ratio. In an embodiment wherein an ironsalt and a pyridine bisimine are continuously introduced into a reactionzone, the oligomer product can be formed at, the reaction zone can have,or the reaction zone can operate at a specified iron salt to pyridinebisimine equivalent ratio. In other embodiments, these processes canoptionally continuously introduce hydrogen into the reaction zone. Inembodiments utilizing hydrogen, the oligomer product can be formed at,the reaction zone can have, or the reaction zone can operate at aspecified hydrogen partial pressure. Generally, the pyridine bisimineiron salt complex, the pyridine bisimine, the iron salt, theorganoaluminum compound, the organic reaction medium, the reaction zone,the specified iron of the pyridine bisimine iron salt complexconcentration, the specified aluminum of the organo aluminum compound toiron of the pyridine bisimine iron salt complex molar ratio, thespecified iron salt to pyridine bisimine equivalent ratio, the specifiedethylene partial pressure, the specified ethylene to organic reactionmedium mass ratio, the specified average temperature, the specifiedaluminum of the organoaluminum compound concentration, the specifiedethylene to organic reaction medium mass ratio, the specified hydrogenpartial pressure, and the specified organic reaction medium, whereapplicable, are independent elements of process described herein and areindependently described herein. These independently described processelements can be utilized in any combination, and without limitation tofurther described the processes provided herein.

In any aspect or embodiment of the processes described herein, theoligomer product formed in the reaction zone can have a specifiedSchultz-Flory K value and/or can have a molecular weight distributionsuch that a specified amount of the oligomer product adhering to thereaction zone wall comprises polyethylene having an M_(W) greater than1000 g/mol. In any aspect or embodiment of the processes describedherein, the reaction zone can be online a specified amount of time.

In various aspects and embodiments, a pyridine bisimine or a pyridinebisimine iron salt complex can be utilized in the processes describedherein. Generally, the pyridine bisimine or the pyridine bisimine ironsalt complex can be any pyridine bisimine or any pyridine bisimine ironsalt complex that when contacted with ethylene and any other appropriatereagent(s) under the appropriate conditions can form an oligomerproduct. Generally, the pyridine bisimine and the iron salt of thepyridine bisimine iron salt complex are independent elements of thepyridine bisimine iron salt complex and are independently disclosedherein. The independent descriptions of the pyridine bisimine and theiron salt of the pyridine bisimine iron salt complex can be used withoutlimitation and in any combination to further describe the pyridinebisimine iron salt complex that can be utilized in aspects and/orembodiments of the processes described herein. In an embodiment, thepyridine bisimine or the pyridine bisimine of the pyridine bisimine ironsalt complex can comprise only one pyridine bisimine group; oralternatively, the pyridine bisimine can comprise only two pyridinebisimine groups.

In an aspect, the pyridine bisimine or the pyridine bisimine of thepyridine bisimine iron salt complex can have Structure PBI I orStructure PBI II; alternatively, Structure PBI I; or alternatively,Structure PBI II. In an aspect, the pyridine bisimine iron salt complexcan have Structure PBIFe I or Structure PBIFe II; alternatively,Structure PBIFe I; or alternatively, Structure PBIFe II.

R¹, R², R³, R⁴, R⁵, R⁶, and R⁷ of the pyridine bisimine having StructurePBI I or the pyridine bisimine iron salt complex having Structure PBIFeI are independent elements of the pyridine bisimine having Structure PBII and the pyridine bisimine iron salt complex having Structure PBIFe Iand are independently described herein. The independent descriptions ofR¹, R², R³, R⁴, R⁵, R⁶, and R⁷ can be utilized without limitation, andin any combination, to further describe the pyridine bisimine havingStructure PBI I and/or the pyridine bisimine iron salt complex havingStructure PBIFe I. Similarly, R², R⁶, R⁷, L¹, and L² of the pyridinebisimine having Structure PBI II or the pyridine bisimine iron saltcomplex having Structure PBIFe II are independent elements of thepyridine bisimine having Structure PBI II and the pyridine bisimine ironsalt complex having Structure PBIFe II and are independently describedherein. The independent descriptions of R², R⁶, R⁷, L¹, and L² can beutilized without limitation, and in any combination, to further describethe pyridine bisimine having Structure PBI II and/or the pyridinebisimine iron salt complex having Structure PBIFe II. Additionally, theiron salt, FeX_(n), is independently described herein can be combined,without limitation, with the independently described R¹, R², R³, R⁴, R⁵,R⁶, R⁷, L¹, and L² to further describe the appropriate pyridine bisimineiron salt complex structure described herein which have an R¹, R², R³,R⁴, R⁵, R⁶, R⁷, L¹, and/or L².

Generally, R¹, R², and/or R³ of the respective pyridine bisimines andpyridine bisimine iron salt complexes, which have an R¹, R², and/or R³,independently can be hydrogen, an inert functional group, or an organylgroup; alternatively, hydrogen or an organyl group; alternatively, aninert functional group or an organyl group; alternatively, hydrogen, aninert functional group, or an organyl group consisting essentially ofinert functional groups; alternatively, hydrogen or an organyl groupconsisting essentially of inert functional groups; alternatively, aninert functional group or an organyl group consisting essentially ofinert functional groups; alternatively, hydrogen, an inert functionalgroup, or a hydrocarbyl group; alternatively, hydrogen or a hydrocarbylgroup; alternatively, an inert functional group or a hydrocarbyl group;alternatively, hydrogen or an inert functional group; alternatively,hydrogen; alternatively, an organyl group; alternatively, organyl groupconsisting essentially of inert functional groups; or alternatively, ahydrocarbyl group. In any aspect and/or embodiment disclosed herein, theR¹, R², and/or R³ organyl groups of the pyridine bisimines and/orpyridine bisimine iron salt complexes which have an R¹, R², and/or R³group, independently can be a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or aC₁ to C₅ organyl group. In any aspect or embodiment disclosed herein,the R¹, R², and/or R³ organyl groups consisting essentially of inertfunctional groups, of the pyridine bisimines and/or pyridine bisimineiron salt complexes which have an R¹, R², and/or R³ group, independentlycan be a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ to C₅ organylgroup consisting essentially of inert functional groups. In any aspectand/or embodiment disclosed herein, the R¹, R², and/or R³ hydrocarbylgroups of the pyridine bisimines and/or pyridine bisimine iron saltcomplexes which have an R¹, R², and/or R³ group, independently can be aC₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ to C₅ hydrocarbyl group.

In any aspect and/or embodiment disclosed herein, the R¹, R², and/or R³hydrocarbyl groups of the pyridine bisimines and pyridine bisimine ironsalt complexes which have an R¹, R², and/or R³ group, independently canbe a C₁ to C₂₀, a C₁ to C₁₀, or a C₁ to C₅ alkyl group. In anembodiment, the R¹, R², and/or R³ alkyl groups of the pyridine bisiminesand pyridine bisimine iron salt complexes which have an R¹, R², and/orR³ group, independently can be a methyl group, an ethyl group, a propylgroup, a butyl group, a pentyl group, a hexyl group, a heptyl group, oran octyl group. In some embodiments, the R¹, R², and/or R³ alkyl groupsof the pyridine bisimines and pyridine bisimine iron salt complexeswhich have an R¹, R², and/or R³ group, independently can be a methylgroup, an ethyl group, an iso-propyl (2-propyl) group, a tert-butyl(2-methyl-2-propyl) group, or a neopentyl (2,2-dimethyl-1-propyl) group;alternatively, a methyl group; alternatively, an ethyl group;alternatively, a n-propyl (1-propyl) group; alternatively, an iso-propyl(2-propyl) group; alternatively, a tert-butyl (2-methyl-2-propyl) group;or alternatively, a neopentyl (2,2-dimethyl-1-propyl) group.

In a particular aspect, R¹, R², and/or R³ of the pyridine bisimineswhich have an R¹, R², and/or R³ group, each can be hydrogen. In theseaspects, the pyridine bisimine can have Structure PBI III or StructurePBI IV; alternatively, Structure PBI III; or alternatively, StructurePBI IV. Similarly, in a particular aspect, R¹, R², and R³ of thepyridine bisimine iron salt complexes which have an R¹, R², and/or R³group, each can be hydrogen. In these aspects, the pyridine bisimineiron salt complexes can have Structure PBIFe III or Structure PBIFe IV;alternatively, Structure PBIFe III; or alternatively, Structure PBIFeIV.

R⁴, R⁵, R⁶, and R⁷ of the pyridine bisimine having Structure PBI III orthe pyridine bisimine iron salt complex having Structure PBIFe III areindependent elements of the pyridine bisimine having Structure PBI IIIand the pyridine bisimine iron salt complex having Structure PBIFe IIIand are independently described herein. The independent descriptions ofR⁴, R⁵, R⁶, and R⁷ can be utilized without limitation, and in anycombination, to further describe the pyridine bisimine having StructurePBI III and/or the pyridine bisimine iron salt complex having StructurePBIFe III. Similarly, R⁶, R⁷, L¹, and L² of the pyridine bisimine havingStructure PBI IV or the pyridine bisimine iron salt complex havingStructure PBIFe IV are independent elements of the pyridine bisiminehaving Structure PBI IV and the pyridine bisimine iron salt complexhaving Structure PBIFe IV and are independently described herein. Theindependent descriptions of R⁶, R⁷, L¹, and L² can utilized withoutlimitation, and in any combination, to further describe the pyridinebisimine having Structure PBI IV and/or the pyridine bisimine iron saltcomplex having Structure PBIFe IV. Additionally, the iron salt, FeX_(n),is independently described herein and can be combined, withoutlimitation, with the independently described R⁴, R⁵, R⁶, R⁷, L¹, and L²to further describe the appropriate pyridine bisimine iron salt complexstructure described herein which have an R⁴, R⁵, R⁶, R⁷, L¹, and/or L².

Generally, R⁴ and/or R⁵ of the pyridine bisimines and pyridine bisimineiron salt complexes, which have an R⁴ and/or R⁵, independently can behydrogen or an organyl group; alternatively, hydrogen or an organylgroup consisting essentially of inert functional groups; alternatively,hydrogen and a hydrocarbyl group; alternatively, hydrogen;alternatively, an organyl group; alternatively, an organyl groupconsisting essentially of inert functional groups; or alternatively, ahydrocarbyl group. In any aspect and/or embodiment disclosed herein, theR⁴ and/or R⁵ organyl groups of the pyridine bisimines and pyridinebisimine iron salt complexes which have an R⁴ and/or R⁵ group,independently can be a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ toC₅ organyl group. In any aspect and/or embodiment disclosed herein, theR⁴ and/or R⁵ organyl groups consisting essentially of inert functionalgroups, of the pyridine bisimines and pyridine bisimine iron saltcomplexes which have an R⁴ and/or R⁵ group, independently can be a C₁ toC₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ to C₅ organyl group consistingessentially of inert functional groups. In any aspect and/or embodimentdisclosed herein, the R⁴ and/or R⁵ hydrocarbyl groups of the pyridinebisimines and pyridine bisimine iron salt complexes which have an R⁴and/or R⁵ group, independently can be a C₁ to C₂₀, a C₁ to C₁₅, a C₁ toC₁₀, or a C₁ to C₅ hydrocarbyl group.

In any aspect or embodiment disclosed herein, the R⁴ and/or R⁵hydrocarbyl groups of the pyridine bisimines and pyridine bisimine ironsalt complexes which have an R⁴ and/or R⁵ group, independently can be aC₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ to C₅ alkyl group. In anembodiment, the R⁴ and/or R⁵ alkyl groups of the pyridine bisimines andpyridine bisimine iron salt complexes which have an R⁴ and/or R⁵ group,independently can be a methyl group, an ethyl group, a propyl group, abutyl group, a pentyl group, a hexyl group, a heptyl group, or an octylgroup. In some embodiments, the R⁴ and/or R⁵ alkyl groups of thepyridine bisimines and pyridine bisimine iron salt complexes which havean R⁴ and/or R⁵ group, independently can be a methyl group, an ethylgroup, an iso-propyl (2-propyl) group, a tert-butyl (2-methyl-2-propyl)group, or a neopentyl (2,2-dimethyl-1-propyl) group; alternatively, amethyl group; alternatively, an ethyl group; alternatively, a n-propyl(1-propyl) group; alternatively, an iso-propyl (2-propyl) group;alternatively, a tert-butyl (2-methyl-2-propyl) group; or alternatively,a neopentyl (2,2-dimethyl-1-propyl) group.

In an aspect, R¹ and R⁴ and/or R³ and R⁵ can be joined to form a ring ora ring system containing two carbon atoms of the pyridine group and thecarbon atom of the imine group. In such aspects, L¹ represents thejoined R³ and R⁵ while L² represents the joined R¹ and R⁴. Generally, L¹and/or L² of a pyridine bisimine or pyridine bisimine iron salt complexhaving an L¹ and/or L² independently can be an organylene group;alternatively, an organylene group consisting essentially of inertfunctional groups; or alternatively, a hydrocarbylene group. In anyaspect or embodiment disclosed herein, the L¹ and/or L² organylenegroups of a pyridine bisimine or pyridine bisimine iron salt complexwhich have an L¹ and/or L² group, independently can be a C₂ to C₂₀, a C₂to C₁₅, a C₂ to C₁₀, or a C₂ to C₅ organylene group. In any aspect orembodiment disclosed herein, the L¹ and/or L² organylene groupsconsisting essentially of inert functional groups of a pyridine bisimineor pyridine bisimine iron salt complex which have an L¹ and/or L² group,independently can be a C₂ to C₂₀, a C₂ to C₁₅, a C₂ to C₁₀, oralternatively, a C₂ to C₅ organylene group consisting essentially ofinert functional groups. In any aspect or embodiment disclosed herein,the L¹ and/or L² hydrocarbylene groups of a pyridine bisimine orpyridine bisimine iron salt complex which have an L¹ and/or L² group,independently can be a C₂ to C₂₀, a C₂ to C₁₅, a C₂ to C₁₀, or a C₂ toC₅ hydrocarbylene group. In any aspect or embodiments disclosed herein,the L¹ and/or L² hydrocarbylene groups of the pyridine bisimines andpyridine bisimine iron salt complexes which have an L¹ and/or L²,independently can be a C₂ to C₂₀, a C₂ to C₁₀, or a C₂ to C₅ alkylenegroup. In any aspect or embodiment where the pyridine bisimine or thepyridine bisimine iron salt complex has an L¹ and an L² group, L¹ and L²can be different; or alternatively, L¹ and L² can be the same.

In an aspect, L¹ and/or L² independently can have the structure—(C(R¹¹)₂)_(p)—. Generally, R¹¹ and p are independent features of L¹and/or L² having the structure —(C(R¹¹)₂)_(p)— and are independentlydescribed herein. The independent descriptions of R¹¹ and p can beutilized without limitation, and in any combination, to describe L¹and/or L² having the structure —(CR¹¹)_(p)— and can be further utilizedto describe the pyridine bisimines and/or the pyridine bisimine ironsalt complexes which have an L¹ and/or L². In an embodiment, each R¹¹independently can be hydrogen, an inert functional group, or ahydrocarbyl group; alternatively, hydrogen or a hydrocarbyl group;alternatively, hydrogen; or alternatively, a hydrocarbyl group. Generaland specific inert functional groups and hydrocarbyl groups areindependently described herein (e.g., as potential substituent groups)and these descriptions can be utilized without limitation to furtherdescribe L¹ and L². In an aspect, each p independently can be an integerfrom 2 to 5; alternatively, an integer from 2 to 3; alternatively, 2; oralternatively, 3. In a non-limiting embodiment, L¹ and L² independentlycan be —CH₂CH₂—, —CH₂CH₂CH₂—, —CH(CH₃)CH₂—, —C(CH₃)₂—, or—CH₂CH₂CH₂CH₂—; alternatively, —CH₂CH₂— or —CH₂CH₂CH₂—; alternatively,—CH₂CH₂—; or alternatively, —CHCH₂CH₂—. In an embodiment, L¹ and L² canbe different. In other embodiments, L¹ and L² can be the same.

Generally, R⁶ and/or R⁷ of the pyridine bisimines and the pyridinebisimine iron salt complexes independently can be an aryl group, asubstituted aryl group, a phenyl group, or a substituted phenyl group;alternatively, aryl group or a substituted aryl group; alternatively, aphenyl group or a substituted phenyl group; alternatively, an arylgroup; alternatively, a substituted aryl group; alternatively, a phenylgroup; or alternatively, a substituted phenyl group. In any aspectand/or embodiment disclosed herein, the R⁶ and/or R⁷ aryl groups of thepyridine bisimines and/or pyridine bisimine iron salt complexesindependently can be a C₆ to C₂₀, a C₆ to C₁₅, or a C₆ to C₁₀ arylgroup. In any aspect and/or embodiment disclosed herein, the R⁶ and/orR⁷ substituted aryl groups of the pyridine bisimines and/or pyridinebisimine iron salt complexes independently can be a C₆ to C₂₀, a C₆ toC₁₅, or a C₆ to C₁₀ substituted aryl group. In any aspect or embodimentdisclosed herein, the R⁶ and/or R⁷ substituted phenyl groups of thepyridine bisimines and/or pyridine bisimine iron salt complexesindependently can be a C₆ to C₂₀, a C₆ to C₁₅, or a C₆ to C₁₅substituted phenyl group. Each substituent of a substituted aryl group(general or specific) or a substituted phenyl group (general orspecific) which can be utilized as R⁶ and/or R⁷ can be a halide, analkyl group, or a hydrocarboxy group; alternatively, a halide or analkyl group; alternatively, a halide or a hydrocarboxy group;alternatively, an alkyl group or a hydrocarboxy group; alternatively, ahalide; alternatively, an alkyl group; or alternatively, a hydrocarboxygroup. Halides, alkyl groups (general and specific), and hydrocarboxygroups (general and specific) that can be utilized as substituents areindependently disclosed herein and can be utilized without limitation,and in any combination, to further describe R⁶ and/or R⁷ of the pyridinebisimines and the pyridine bisimine iron salt complexes.

In an embodiment, each substituted phenyl group which can be utilized asR⁶ and/or R⁷ of the pyridine bisimines and the pyridine bisimine ironsalt complexes independently can be a substituted phenyl groupcomprising a substituent at the 2-position, a substituted phenyl groupcomprising a substituent at the 3-position, a substituted phenyl groupcomprising a substituent at the 4-position, a substituted phenyl groupcomprising substituents at the 2- and 3-positions, a substituted phenylgroup comprising substituents at the 2- and 4-positions, a substitutedphenyl group comprising substituents at the 2- and 5-positions, asubstituted phenyl group comprising substituents at the 3- and5-positions, a substituted phenyl group comprising substituents at the2- and 6-positions, or a substituted phenyl group comprisingsubstituents at the 2-, 4-, and 6-positions; alternatively, asubstituted phenyl group comprising a substituent at the 2-position, asubstituted phenyl group comprising a substituent at the 4-position, asubstituted phenyl group comprising substituents at the 2- and4-positions, a substituted phenyl group comprising substituents at the2- and 6-positions, or a substituted phenyl group comprisingsubstituents at the 2-, 4-, and 6-position; alternatively, a substitutedphenyl group comprising substituents at the 2- and 6-positions or asubstituted phenyl group comprising substituents at the 2-, 4-, and6-positions; alternatively, a substituted phenyl group comprising asubstituent at the 2-position; alternatively, a substituted phenyl groupcomprising a substituent at the 3-position; alternatively, a substitutedphenyl group comprising a substituent at the 4-position; alternatively,a substituted phenyl group comprising substituents at the 2- and3-positions; alternatively, a substituted phenyl group comprisingsubstituents at the 2- and 4-positions; alternatively, a substitutedphenyl group comprising substituents at the 2- and 5-positions;alternatively, a substituted phenyl group comprising substituents at the3- and 5-positions; alternatively, a substituted phenyl group comprisingsubstituents at the 2- and 6-position; or alternatively, a substitutedphenyl group comprising substituents at the 2-, 4-, and 6-positions. Insome embodiments, each substituted phenyl group which can be utilized asR⁶ and/or R⁷ of the pyridine bisimines and the pyridine bisimine ironsalt complexes independently can be selected such that (1) one, or twoof the 2- and 6-positions of the R⁶ and R⁷ phenyl groups and/orsubstituted phenyl groups independently can be a halogen, a primarycarbon atom group, or a secondary carbon atom group and the remainder ofthe positions of the R⁶ and R⁷ phenyl groups and/or substituted phenylgroups can be hydrogen, (2) one of the 2- and 6-positions of the R⁶ andR⁷ phenyl groups and/or substituted phenyl groups can be a tertiarycarbon atom group, none, one, or two of the 2- and 6-positions of the R⁶and R⁷ phenyl groups and/or substituted phenyl groups independently canbe a halogen, a primary carbon atom group or a secondary carbon atomgroup, and the remainder of the positions of the R⁶ and/or R⁷ phenylgroups and/or substituted phenyl groups can be hydrogen, (3) two of the2- and 6-positions of the R⁶ and R⁷ phenyl groups and/or substitutedphenyl groups can be a tertiary carbon atom group, none, or one of the2- and 6-positions of the R⁶ and R⁷ phenyl groups and/or substitutedphenyl groups independently can be a halogen, a primary carbon atomgroup, or a secondary carbon atom group, and the remainder of thepositions of the R⁶ and R⁷ phenyl groups and/or substituted phenylgroups can be hydrogen, (4) one or two of the 2- and 6-positions of theR⁶ and R⁷ phenyl groups and/or substituted phenyl groups can be atertiary carbon atom group and the remainder of the 2- and 6-positionsof the R⁶ and R⁷ phenyl groups and/or substituted phenyl groups can behydrogen, 5) one or two of the 2- and 6-positions of the R⁶ and R⁷phenyl groups and/or substituted phenyl groups can be a quaternarycarbon atom group and the remainder of the 2- and 6-positions of the R⁶and R⁷ phenyl groups and/or substituted phenyl groups can be hydrogen,or 6) all four of the 2- and 6-positions of the R⁶ and R⁷ substitutedphenyl groups can be fluorine. Each substituent of a substituted arylgroup (general or specific) or a substituted phenyl group (general orspecific) which can be utilized as R⁶ and/or R⁷ can be a halide, analkyl group, or a hydrocarboxy group; alternatively, a halide or analkyl group; alternatively, a halide and a hydrocarboxy group;alternatively, an alkyl group or a hydrocarboxy group; alternatively, ahalide; alternatively, an alkyl group; or alternatively, a hydrocarboxygroup. Halides, alkyl groups (general and specific), and hydrocarboxygroups (general and specific) that can be utilized as substituents areindependently disclosed herein and can be utilized without limitation,and in any combination, to further describe R⁶ and/or R⁷ of the pyridinebisimines and the pyridine bisimine iron salt complexes. Further, onehaving ordinary skill in the art can recognize the independentlydescribed substituted phenyl group(s) which meet the criteria for asubstituted phenyl groups (e.g., primary, secondary, tertiary, andquaternary carbon atom groups, among other criteria) and choose theappropriate substituted phenyl group(s) to meet any particular criteriafor a substituted phenyl group(s) for a pyridine bisimine and/or apyridine bisimine iron salt described herein.

In an embodiment, each substituted phenyl group which can be utilized asR⁶ and/or R⁷ of the pyridine bisimines and the pyridine bisimine ironsalt complexes independently can be a 2-substituted phenyl group, a3-substituted phenyl group, a 4-substituted phenyl group, a2,3-disubstituted phenyl group, a 2,4-disubstituted phenyl group, a2,5-disubstituted phenyl group, a 3,5-disubstituted phenyl group, a2,6-disubstituted phenyl group, or a 2,4,6-trisubsituted phenyl group;alternatively, a 2-substituted phenyl group, a 4-substituted phenylgroup, a 2,4-disubstituted phenyl group, a 2,6-disubstituted phenylgroup, or a 2,4,6-trisubsituted phenyl group; alternatively, a2,6-disubstituted phenyl group, or a 2,4,6-trisubsituted phenyl group;alternatively, a 2-substituted phenyl group; alternatively, a4-substituted phenyl group; alternatively, a 2,3-disubstituted phenylgroup; alternatively, a 2,4-disubstituted phenyl group; alternatively, a2,5-disubstituted phenyl group; alternatively, a 3,5-disubstitutedphenyl group; alternatively, a 2,6-disubstituted phenyl group; oralternatively, a 2,4,6-trisubsituted phenyl group. In some embodiments,each substituted phenyl group which can be utilized as R⁶ and/or R⁷ ofthe pyridine bisimines and the pyridine bisimine iron salt complexesindependently can be selected such that (1) one, two, or three of the 2-and 6-positions of the R⁶ and R⁷ phenyl groups and/or substituted phenylgroups independently can be a halogen, a primary carbon atom group, or asecondary carbon atom group and the remainder of the 2- and 6-positionsof the R⁶ and R⁷ phenyl groups and/or substituted phenyl groups can behydrogen, (2) one of the 2- and 6-positions of the R⁶ and R⁷ phenylgroups and/or substituted phenyl groups can be a tertiary carbon atomgroup, none, one, or two of the 2- and 6-positions of the R⁶ and R⁷phenyl groups and/or substituted phenyl groups independently can be ahalogen, a primary carbon atom group or a secondary carbon atom group,and the remainder of the 2- and 6-positions of the R⁶ and R⁷ phenylgroups and/or substituted phenyl groups can be hydrogen, (3) two of the2- and 6-positions of the R⁶ and R⁷ phenyl groups and/or substitutedphenyl groups can be a tertiary carbon atom group, none, or one of the2- and 6-positions of the R⁶ and R⁷ phenyl groups and/or substitutedphenyl groups independently can be a halogen, a primary carbon atomgroup, or a secondary carbon atom group, and the remainder of the 2- and6-positions of the R⁶ and R⁷ phenyl groups and/or substituted phenylgroups can be hydrogen, (4) one or two of the 2- and 6-positions of theR⁶ and R⁷ phenyl groups and/or substituted phenyl groups can be atertiary carbon atom group and the remainder of the 2- and 6-positionsof the R⁶ and R⁷ phenyl groups and/or substituted phenyl groups can behydrogen, 5) one or two of the 2- and 6-positions of the R⁶ and R⁷phenyl groups and/or substituted phenyl groups can be a quaternarycarbon atom group and the remainder of the 2- and 6-positions of the R⁶and R⁷ phenyl groups and/or substituted phenyl groups can be hydrogen,or 6) all four of the 2- and 6-positions of the R⁶ and R⁷ substitutedphenyl groups can be fluorine. Each substituent of a substituted arylgroup (general or specific) or a substituted phenyl group (general orspecific) which can be utilized as R⁶ and/or R⁷ can be a halide, analkyl group, or a hydrocarboxy group; alternatively, a halide or analkyl group; alternatively, a halide and a hydrocarboxy group;alternatively, an alkyl group or a hydrocarboxy group; alternatively, ahalide; alternatively, an alkyl group; or alternatively, a hydrocarboxygroup. Halides, alkyl groups (general and specific), and hydrocarboxygroups (general and specific) that can be utilized as substituents areindependently disclosed herein and can be utilized without limitation,and in any combination, to further describe R⁶ and/or R⁷ of the pyridinebisimines and the pyridine bisimine iron salt complexes. Further, onehaving ordinary skill in the art can recognize the independentlydescribed substituted phenyl group(s) which meet the criteria for asubstituted phenyl groups (e.g., primary, secondary, tertiary, andquaternary carbon atom groups, among other criteria) and choose theappropriate substituted phenyl group(s) to meet any particular criteriafor a substituted phenyl group(s) for a pyridine bisimine and/or apyridine bisimine iron salt described herein.

In an embodiment, R⁶ and/or R⁷ of the pyridine bisimines and thepyridine bisimine iron salt complexes independently can a phenyl group,a 2-methylphenyl group, a 2-ethylphenyl group, a 2-isopropylphenylgroup, a 2-tert-butylphenyl group, a 2-(phenyl)phenyl group, a2-trifluoromethylphenyl group, a 2-fluorophenyl group, a 2-methoxyphenylgroup, a 4-methylphenyl group, a 4-ethylphenyl group, a4-isopropylphenyl group, a 4-tert-butylphenyl group, a 4-fluorophenylgroup, a 4-trifluoromethylphenyl group, a 4-methoxyphenyl group, a2,3-dimethyl phenyl group, 2-fluoro-3-methylphenyl group, a2,4-dimethylphenyl group, a 2,4-diethylphenyl group, a2,4-diisopropylphenyl group, a 2,4-di-tert-butylphenyl group, a2-fluoro-4-methylphenyl group, a 2,5-dimethylphenyl group, a2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a2,6-diisopropylphenylgroup, a 2,6-diphenylphenyl group, a2-fluoro-6-methylphenyl group, a 2,6-bis(trifluoromethyl)phenyl group, a2,6-difluorophenyl group, a 3,5-dimethylphenyl group, a3,5-diethylphenyl group, a 3,5-diisopropylphenyl group, a3,5-di-tert-butylphenyl group, a 3,5-di(trifluoromethyl)phenyl group, ora 2,4,6-trimethylphenyl group. In some embodiments, R⁶ and/or R⁷ of thepyridine bisimines and the pyridine bisimine iron salt complexesindependently can be selected such that (1) one, two, or three of the 2-and 6-positions of the R⁶ and R⁷ phenyl groups and/or substituted phenylgroups independently can be a halogen, a primary carbon atom group, or asecondary carbon atom group and the remainder of the 2- and 6-positionsof the R⁶ and R⁷ phenyl groups and/or substituted phenyl groups can behydrogen, (2) one of the 2- and 6-positions of the R⁶ and R⁷ phenylgroups and/or substituted phenyl groups can be a tertiary carbon atomgroup, none, one, or two of the 2- and 6-positions of the R⁶ and R⁷phenyl groups and/or substituted phenyl groups independently can be ahalogen, a primary carbon atom group or a secondary carbon atom group,and the remainder of the 2- and 6-positions of the R⁶ and R⁷ phenylgroups and/or substituted phenyl groups can be hydrogen, (3) two of the2- and 6-positions of the R⁶ and R⁷ phenyl groups and/or substitutedphenyl groups can be a tertiary carbon atom group, none, or one of the2- and 6-positions of the R⁶ and R⁷ phenyl groups and/or substitutedphenyl groups independently can be a halogen, a primary carbon atomgroup, or a secondary carbon atom group, and the remainder of the 2- and6-positions of the R⁶ and R⁷ phenyl groups and/or substituted phenylgroups can be hydrogen, (4) one or two of the 2- and 6-positions of theR⁶ and R⁷ phenyl groups can be a tertiary carbon atom group and theremainder of the 2- and 6-positions of the R⁶ and R⁷ phenyl groupsand/or substituted phenyl groups can be hydrogen, 5) one or two of the2- and 6-positions of the R⁶ and R⁷ phenyl groups and/or substitutedphenyl groups can be a quaternary carbon atom group and the remainder ofthe 2- and 6-positions of the R⁶ and R⁷ phenyl groups and/or substitutedphenyl groups can be hydrogen, or 6) all four of the 2- and 6-positionsof the R⁶ and R⁷ substituted phenyl groups can be fluorine. One havingordinary skill in the art can recognize the independently describedsubstituted phenyl group(s) which meet the criteria for a substitutedphenyl groups (e.g., primary, secondary, and tertiary carbon atomgroups, among other criteria) and choose the appropriate substitutedphenyl group(s) to meet any particular criteria for a substituted phenylgroup(s) for a pyridine bisimine and/or a pyridine bisimine iron saltdescribed herein.

In an aspect, the pyridine bisimine can comprise, consist essentiallyof, or can be, a 2,6-bis[(arylimine)hydrocarbyl]pyridine, abis[(substituted arylimine)hydrocarbyl]pyridine, or a[(arylimine)hydrocarbyl],[(substituted arylimine)hydrocarbyl]pyridine;alternatively, a 2,6-bis[(arylimine)hydrocarbyl]pyridine; alternatively,a bis[(substituted arylimine)hydrocarbyl]pyridine; or alternatively, a[(arylimine)hydrocarbyl],[(substituted arylimine)hydrocarbyl]pyridine.In an aspect, the pyridine bisimine iron salt complex can comprise,consist essentially of, or can be, a2,6-bis[(arylimine)hydrocarbyl]pyridine iron salt complex,bis[(substituted arylimine)hydrocarbyl]pyridine iron salt complex, or a[(arylimine)hydrocarbyl],[(substituted arylimine)hydrocarbyl]pyridineiron salt complex; alternatively, a2,6-bis[(arylimine)hydrocarbyl]pyridine iron salt complex;alternatively, a bis[(substituted arylimine)hydrocarbyl]pyridine ironsalt complex; or alternatively, a [(arylimine)hydrocarbyl],[(substitutedarylimine)hydrocarbyl]pyridine iron salt complex. In some embodiments,the aryl groups of the 2,6-bis[(arylimine)hydrocarbyl]pyridine or the2,6-bis[(arylimine)hydrocarbyl]pyridine iron salt complex can be thesame or can be different; alternatively, the same; or alternatively,different. In some embodiments, the substituted aryl groups of the2,6-bis[(substituted arylimine)hydrocarbyl]pyridine or the2,6-bis[(substituted arylimine)hydrocarbyl]pyridine iron salt complexcan be the same or can be different; alternatively, the same; oralternatively, different. In an embodiment, the pyridine bisimine or thepyridine bisimine of the pyridine bisimine iron salt complex cancomprise, consist essentially of, or can be,2,6-bis[(arylimine)hydrocarbyl]pyridine, a bis[(substitutedarylimine)hydrocarbyl]pyridine, and/or a[(arylimine)hydrocarbyl],[(substituted arylimine)hydrocarbyl]pyridinewherein 1) one, two, or three of the aryl groups and/or substituted arylgroups positions ortho to the carbon atom attached to the imine nitrogenindependently can be a halogen, a primary carbon atom group, or asecondary carbon atom group and the remainder of the aryl groups and/orsubstituted aryl groups positions ortho to the carbon atom attached tothe imine nitrogen can be hydrogen, 2) one of the aryl groups and/orsubstituted aryl groups positions ortho to the carbon atom attached tothe imine nitrogen can be a tertiary carbon atom group, none, one, ortwo of the aryl groups and/or substituted aryl groups positions ortho tothe carbon atom attached to the imine nitrogen independently can be ahalogen, a primary carbon atom group or a secondary carbon atom group,and the remainder of the aryl groups and/or substituted aryl groupspositions ortho to the carbon atom attached to the imine nitrogen can behydrogen, 3) two of the aryl groups and/or substituted aryl groupspositions ortho to the carbon atom attached to the imine nitrogenindependently can be a tertiary carbon atom group, none, or one of thearyl groups and/or substituted aryl groups positions ortho to the carbonatom attached to the imine nitrogen independently can be a halogen, aprimary carbon atom group, or a secondary carbon atom group, and theremainder of the aryl groups and/or substituted aryl groups positionsortho to the carbon atom attached to the imine nitrogen can be hydrogen,4) one or two of the aryl groups and/or substituted aryl groupspositions ortho to the carbon atom attached to the imine nitrogenindependently are a tertiary carbon atom group(s) and the remainder ofthe aryl groups and/or substituted aryl groups positions ortho to thecarbon atom attached to the imine nitrogen can be hydrogen, 5) one ortwo of the aryl groups and/or substituted aryl groups positions ortho tothe carbon atom attached to the imine nitrogen can be a quaternarycarbon atom group and the remainder of the aryl groups and/orsubstituted aryl groups positions ortho to the carbon atom attached tothe imine nitrogen can be hydrogen, or 6) all four of the substitutedaryl groups positions ortho to the carbon atom attached to the iminenitrogen are fluorine. Hydrocarbyl groups (general and specific), arylgroups (general and specific), and substituted aryl groups (general andspecific) are independently described herein. The independentdescriptions of the hydrocarbyl group, aryl groups, and substituted arylgroups can be utilized without limitation, an in any combination, tofurther describe the 2,6-bis[(arylimine)hydrocarbyl]pyridine, thebis[(substituted arylimine)hydrocarbyl]pyridine, or the[(arylimine)hydrocarbyl],[(substituted arylimine)-hydrocarbyl]pyridinewhich can be utilized as the pyridine bisimine or the pyridine bisimineiron salt complex that can be utilized in the processes describedherein. One having ordinary skill in the art can recognize theindependently described aryl group(s) and/or substituted aryl group(s)which meet the criteria for aryl group and/or substituted aryl groups(e.g., primary, secondary, and tertiary carbon atom groups, among othercriteria) and choose the appropriate aryl group(s) and/or substitutedaryl group(s) to meet any particular criteria for the aryl group(s)and/or substituted phenyl group(s) for a pyridine bisimine and/or apyridine bisimine iron salt complex described herein. Further, the ironsalt, FeX_(n), is independently described herein can be combined,without limitation, with the independently described aryl group(s) andsubstituted aryl group(s) to further describe the appropriate pyridinebisimine iron salt complexes which can be utilized in the processesdescribed herein.

In an embodiment, the pyridine bisimine and/or the pyridine bisimine ofthe pyridine bisimine iron salt complex can be 2,6-bis[(phenylimine)methyl]pyridine, 2,6-bis[(2-methylphenylimine)methyl]-pyridine,2,6-bis[(2-ethylphenylimine)methyl]pyridine,2,6-bis[(2-isopropylphenylimine)methyl]pyridine,2,6-bis[(2,4-dimethylphenylimine)methyl]pyridine,2,6-bis[(2,6-diethylphenylimine)methyl]pyridine,2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-methylphenylimine)methyl]pyridine,2-[(2,4,6-trimethyl-phenylimine)methyl]-6-[(3,5-dimethylphenylimine)methyl]pyridine, or2-[(2,4,6-trimethylphenylimine)-methyl]-6-[(4-t-butylphenylimine)methyl]pyridine.The iron salt, FeX₁₁, is independently described herein can be combined,without limitation, with the pyridine bisimine(s) to further describethe appropriate pyridine bisimine iron salt complexes which can beutilized in the processes described herein.

Additional descriptions of pyridine bisimine iron salt complexessuitable for use in the present disclosure can be found in U.S. Pat. No.5,955,555, U.S. Pat. No. 6,103,946, U.S. Pat. No. 6,291,733, U.S. Pat.No. 6,489,497, U.S. Pat. No. 6,451,939, U.S. Pat. No. 6,455,660, U.S.Pat. No. 6,458,739, U.S. Pat. No. 6,472,341, U.S. Pat. No. 6,545,108,U.S. Pat. No. 6,559,091, U.S. Pat. No. 6,657,026, U.S. Pat. No.6,683,187, U.S. Pat. No. 6,710,006, U.S. Pat. No. 6,911,505, U.S. Pat.No. 6,911,506, U.S. Pat. No. 7,001,964, U.S. Pat. No. 7,045,632, U.S.Pat. No. 7,056,997, U.S. Pat. No. 7,223,893, U.S. Pat. No. 7,456,284,U.S. Pat. No. 7,683,149, U.S. Pat. No. 7902,415, U.S. Pat. No. 7,994,376and EP 1229020A1.

Generally, the iron salt or the iron salt of the pyridine bisimine ironsalt complex can have the formula FeX_(n). Within the formula of theiron salt having the formula FeX_(n), X represents a monoanionic specie,and n represent the number of monoanionic species (or the iron oxidationstate). Generally, the monoanionic specie, X, and the number of anionicspecies (or the iron oxidation state), n, are independent elements ofthe iron salt and are independently described herein. The iron salthaving the formula FeX_(n) can be described utilizing any aspect orembodiment of the monoanionic specie described herein, and any aspectand/or embodiment of the number of monoanionic species (or ironoxidation state) described herein.

Generally, the number of monoanionic species (or the iron oxidationstate) of the iron salt or the iron salt of the pyridine bisimine ironsalt complex can be any positive value that corresponds to an oxidationstate available to an iron atom. In an embodiment, the number ofmonoanionic species, n, of the iron salt or the iron salt of thepyridine bisimine iron salt complex can be 1, 2 or 3; alternatively, 2or 3; alternatively, 1; alternatively, 2; or alternatively, 3.

Generally, the monoanionic specie, X, of the iron salt or the iron saltof the pyridine bisimine iron salt complex can be any monoanionicspecie. In an embodiment, the monoanionic specie, X, can be a halide, acarboxylate, a β-diketonate, a hydrocarboxide, a nitrate, or a chlorate.In some embodiments, the monoanionic specie, X, of the iron salt or theiron salt of the pyridine bisimine iron salt complex can be a halide, acarboxylate, a β-diketonate, or a hydrocarboxide; or alternatively, ahalide, a carboxylate, or a β-diketonate. In any aspect and/orembodiment, the hydrocarboxide can be an alkoxide, an aryloxide, or anaralkoxide. Generally, hydrocarboxide (and subdivisions ofhydrocarboxide) are the anion analogues of the hydrocarboxy group. Inother embodiments, the monoanionic specie, X, of the iron salt or theiron salt of the pyridine bisimine iron salt complex can be a halide, acarboxylate, a β-diketonate, or an alkoxide. In other embodiments, themonoanionic specie, X, of the iron salt or the iron salt of the pyridinebisimine iron salt complex can be a halide; alternatively, acarboxylate; alternatively, a β-diketonate; alternatively, ahydrocarboxide; alternatively, an alkoxide; or alternatively, anaryloxide.

Generally, each halide monoanionic specie, X, of the iron salt or theiron salt of the pyridine bisimine iron salt complex independently canbe fluorine, chlorine, bromine, or iodine; or alternatively, chlorine,bromine, or iodine. In an embodiment, each halide monoanionic specie, X,of the iron salt or the iron salt of the pyridine bisimine iron saltcomplex can be chlorine; alternatively, bromine; or alternatively,iodine.

Generally, each carboxylate monoanionic specie, X, of the iron salt orthe iron salt of the pyridine bisimine iron salt complex can be a C₁ toC₂₀ carboxylate; or alternatively, a C₁ to C₁₀ carboxylate. In anembodiment, each carboxylate of the iron salt or the iron salt of thepyridine bisimine iron salt complex independently can be acetate, apropionate, a butyrate, a pentanoate, a hexanoate, a heptanoate, anoctanoate, a nonanoate, a decanoate, an undecanoate, or a dodecanoate;or alternatively, a pentanoate, a hexanoate, a heptanoate, an octanoate,a nonanoate, or a decanoate. In some embodiments, each carboxylatemonoanionic specie, X, of the iron salt or the iron salt of the pyridinebisimine iron salt complex independently can be acetate, propionate,n-butyrate, valerate (n-pentanoate), neo-pentanoate, capronate(n-hexanoate), n-heptanoate, caprylate (n-octanoate), 2-ethylhexanoate,n-nonanoate, caprate (n-decanoate), n-undecanoate, or laurate(n-dodecanoate); alternatively, valerate (n-pentanoate), neo-pentanoate,capronate (n-hexanoate), n-heptanoate, caprylate (n-octanoate),2-ethylhexanoate, n-nonanoate, or caprate (n-decanoate; alternatively,n-heptanoate; alternatively, caprylate (n-octanoate); or alternatively,2-ethylhexanoate. In some embodiments, the carboxylate can be triflate(trifluoroacetate).

Generally, each β-diketonate monoanionic specie, X, of the iron salt orthe iron salt of the pyridine bisimine iron salt complex can be a C₁ toC₂₀ a β-diketonate; or alternatively, a C₁ to C₁₀ β-diketonate. In anembodiment, each β-diketonate monoanionic specie, X, of the iron salt orthe iron salt of the pyridine bisimine iron salt complex independentlycan be acetylacetonate (i.e., 2,4-pentanedionate),hexafluoroacetylacetonate (i.e.,1,1,1,5,5,5-hexafluoro-2,4-pentanedionate), or benzoylacetonate;alternatively, acetylacetonate; alternatively, hexafluoroacetylacetone;or alternatively, benzoylacetonate.

Generally, each hydrocarboxide monoanionic specie, X, of the iron saltor the iron salt of the pyridine bisimine iron salt complex can be anyC₁ to C₂₀ hydrocarboxide; or alternatively, any C₁ to C₁₀hydrocarboxide. In an embodiment, each hydrocarboxide monoanionicspecie, X, of the iron salt or the iron salt of the pyridine bisimineiron salt complex can be a C₁ to C₂₀ alkoxide; alternatively, a C₁ toC₁₀ alkoxide; alternatively, a C₆ to C₂₀ aryloxide; or alternatively, aC₆ to C₁₀ aryloxide. In an embodiment, each alkoxide monoanionic specie,X, of the iron salt or the iron salt of the pyridine bisimine iron saltcomplex independently can be methoxide, ethoxide, a propoxide, or abutoxide. In some embodiments, each alkoxide monoanionic specie, X, ofthe iron salt or the iron salt of the pyridine bisimine iron saltcomplex independently can be methoxide, ethoxide, isopropoxide, ortert-butoxide; alternatively, methoxide; alternatively, an ethoxide;alternatively, an iso-propoxide; or alternatively, a tert-butoxide. Inan aspect, each aryloxide monoanionic specie, X, of the iron salt or theiron salt of the pyridine bisimine iron salt complex independently canbe phenoxide.

In an embodiment, the iron salt or the iron salt of the pyridinebisimine iron salt complex can comprise, or consist essentially of, orcan be an iron halide, an iron acetylacetonate, an iron carboxylate, orany combination thereof. In some embodiments, the iron salt or the ironsalt of the pyridine bisimine iron salt complex can comprise, consistessentially of, or can be, iron(II) fluoride, iron(III) fluoride,iron(II) bromide, iron(III) bromide, iron(II) iodide, iron(III) iodide,iron(II) acetate, iron(III) acetate, iron(II) acetylacetonate, iron(III)acetylacetonate, iron(II) 2-ethylhexanoate, iron(III) 2-ethylhexanoate,iron(II) triflate, iron(III) triflate, iron(II) nitrate, iron(III)nitrate, or any combination thereof; alternatively, iron(II) chloride,iron(III) chloride, iron(II) acetate, iron(III) acetate, iron(II)acetylacetonate, iron(III) acetylacetonate, or any combination thereof;alternatively, iron(II) chloride, iron(III) chloride, iron(II)acetylacetonate, iron(III) acetylacetonate, or any combination thereof;alternatively, iron(II) chloride; alternatively, iron(III) chloride; oralternatively, iron(II) acetylacetonate.

In an embodiment, the pyridine bisimine iron salt complex can beselected from the group consisting of a 2,6-bis[(phenylimine)methyl]pyridine iron salt complex, a2,6-bis[(2-methylphenylimine)methyl]pyridine iron salt complex, a2,6-bis[(2-ethylphenylimine)methyl]pyridine iron salt complex, a2,6-bis[(2-isopropylphenylimine)methyl]pyridine iron salt complex, a2,6-bis[(2,4-dimethylphenylimine)methyl]pyridine, a2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-methylphenyl-imine)methyl]pyridineiron salt complex, a2-[(2,4,6-trimethylphenylimine)methyl]-6-[(3,5-dimethyl-phenylimine)methyl]pyridineiron salt complex, and a2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-t-butylphenylimine)methyl]pyridineiron salt complex. In another embodiment, the pyridine bisimine ironsalt complex can be selected from the group consisting of a2,6-bis[(phenylimine) methyl]pyridine iron dichloride complex, a2,6-bis[(2-methylphenylimine)methyl]pyridine iron dichloride complex, a2,6-bis[(2-ethylphenylimine)methyl]pyridine iron dichloride complex, a2,6-bis[(2-isopropylphenylimine)-methyl]pyridine iron dichloridecomplex, a 2,6-bis[(2,4-dimethylphenylimine)methyl]pyridine, a2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-methylphenylimine)methyl]pyridineiron dichloride complex, a2-[(2,4,6-trimethylphenylimine)methyl]-6-[(3,5-dimethylphenylimine)methyl]pyridineiron dichloride complex, and a2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-t-butylphenylimine)methyl]pyridineiron dichloride complex. In another embodiment, the pyridine bisimineiron salt complex can be selected from the group consisting of a2,6-bis[(phenylimine) methyl]pyridine iron diacetylacetonate complex, a2,6-bis[(2-methylphenylimine)methyl]pyridine iron diacetylacetonatecomplex, a 2,6-bis[(2-ethylphenylimine)methyl]pyridine irondiacetylacetonate complex, a2,6-bis[(2-isopropylphenylimine)methyl]pyridine iron diacetylacetonatecomplex, a 2,6-bis[(2,4-dimethylphenylimine)methyl]pyridine, a2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-methylphenyl-imine)methyl]pyridineiron diacetylacetonate complex, a2-[(2,4,6-trimethylphenylimine)methyl]-6-[(3,5-dimethylphenylimine)methyl]pyridineiron diacetylacetonate complex, and a2-[(2,4,6-trimethyl-phenylimine)methyl]-6-[(4-t-butylphenylimine)methyl]pyridineiron diacetylacetonate complex.

It should be noted that while not explicitly shown or stated, the ironsalts and/or the pyridine bisimine iron salt complexes can furthercomprise a neutral ligand. While the non-pyridine bisimine neutralligand for the iron salts or the pyridine bisimine iron salt complexesare not shown in the structure or the formulas provided herein, itshould be understood that the iron salts and/or the pyridine bisimineiron salt complexes depictions do not limit the iron salts or thepyridine bisimine iron salt complexes to those not having a non-pyridinebisimine neutral ligand. In fact the iron salts or the pyridine bisimineiron salt complexes which can be utilized in any aspect disclosed hereinor any embodiment disclosed herein can include a non-pyridine bisimineneutral ligand and that these depictions provided herein do not limitiron complexes to those which do not comprise a non-pyridine bisimineneutral ligand regardless of the language utilized to describe the ironcomplexes. Non-pyridine bisimine neutral ligands are provided herein andcan be utilized without limitation to further describe the iron saltsand/or the pyridine bisimine iron salt complexes.

Generally, the neutral ligand, if present, can be any neutral ligandthat forms an isolatable compound with the iron salt or the pyridinebisimine iron salt complex. In an aspect, each neutral ligandindependently can be a nitrile, an ether, or an amine; alternatively, anitrile; alternatively, an ether; or alternatively, an amine. The numberof neutral ligands of the iron salt or the pyridine bisimine iron saltcomplex can be any number that forms an isolatable compound with theiron salts or the pyridine bisimine iron salt complexes. In anembodiment, the number of neutral ligands, if the iron salt or thepyridine bisimine iron salt complex has non-pyridine bisimine neutralligands, can be 1, 2, 3, 4, 5, or 6; alternatively, 1; alternatively, 2;alternatively, 3; alternatively, 4; alternatively, 5; or alternatively,6.

Generally, each nitrile ligand which can be utilized as the non-pyridinebisimine neutral ligand independently can be a C₂ to C₂₀ nitrile; oralternatively, a C₂ to C₁₀ nitrile. In an embodiment, each nitrileligand independently can be a C₂ to C₂₀ aliphatic nitrile, a C₇ to C₂₀aromatic nitrile, a C₈ to C₂₀ aralkane nitrile, or any combinationthereof; alternatively, a C₂ to C₂₀ aliphatic nitrile; alternatively, aC₇ to C₂₀ aromatic nitrile; or alternatively, a C₈ to C₂₀ aralkanenitrile. In some embodiments, each nitrile ligand which can be utilizedas the non-pyridine bisimine neutral ligand independently can be a C₂ toC₁₀ aliphatic nitrile, a C₇ to C₁₀ aromatic nitrile, a C₈ to C₁₀aralkane nitrile, or any combination thereof; alternatively, a C₁ to C₁₀aliphatic nitrile; alternatively, a C₇ to C₁₀ aromatic nitrile; oralternatively, a C₈ to C₁₀ aralkane nitrile. In an embodiment, eachaliphatic nitrile which can be utilized as the non-pyridine bisimineneutral ligand independently can be acetonitrile, propionitrile, abutyronitrile, benzonitrile, or any combination thereof; alternatively,acetonitrile; alternatively, propionitrile; alternatively, abutyronitrile; or alternatively, benzonitrile.

Generally, each ether ligand which can be utilized as the non-pyridinebisimine neutral ligand independently can be a C₂ to C₄₀ ether;alternatively, a C₂ to C₃₀ ether; or alternatively, a C₂ to C₂₀ ether.In an embodiment, each ether ligand which can be utilized as thenon-pyridine bisimine neutral ligand independently can be a C₂ to C₄₀aliphatic ether, a C₃ to C₄₀ aliphatic cyclic ether, a C₄ to C₄₀aromatic cyclic ether; alternatively, a C₂ to C₄₀ aliphatic acyclicether or a C₃ to C₄₀ aliphatic cyclic ether; alternatively, a C₂ to C₄₀aliphatic acyclic ether; alternatively, a C₃ to C₄₀ aliphatic cyclicether; or alternatively, a C₄ to C₄₀ aromatic cyclic ether. In someembodiments, each ether ligand which can be utilized as the non-pyridinebisimine neutral ligand independently can be a C₂ to C₃₀ aliphaticether, a C₃ to C₃₀ aliphatic cyclic ether, a C₄ to C₃₀ aromatic cyclicether; alternatively, a C₂ to C₃₀ aliphatic acyclic ether or a C₃ to C₃₀aliphatic cyclic ether; alternatively, a C₂ to C₃₀ aliphatic acyclicether; alternatively, a C₃ to C₃₀ aliphatic cyclic ether; oralternatively, a C₄ to C₃₀ aromatic cyclic ether. In other embodiments,each ether ligand which can be utilized as the non-pyridine bisimineneutral ligand independently can be a C₂ to C₂₀ aliphatic ether, a C₃ toC₂₀ aliphatic cyclic ether, a C₄ to C₂₀ aromatic cyclic ether;alternatively, a C₂ to C₂₀ aliphatic acyclic ether or a C₃ to C₂₀aliphatic cyclic ether; alternatively, a C₂ to C₂₀ aliphatic acyclicether; alternatively, a C₃ to C₂₀ aliphatic cyclic ether; oralternatively, a C₄ to C₂₀ aromatic cyclic ether. In some embodiments,each ether ligand which can be utilized as the non-pyridine bisimineneutral ligand independently can be dimethyl ether, diethyl ether, adipropyl ether, a dibutyl ether, methyl ethyl ether, a methyl propylether, a methyl butyl ether, tetrahydrofuran, a dihydrofuran,1,3-dioxolane, tetrahydropyran, a dihydropyran, a pyran, a dioxane,furan, benzofuran, isobenzofuran, isobenzofuran, dibenzofuran, diphenylether, a ditolyl ether, or any combination thereof; alternatively,dimethyl ether, diethyl ether, a dipropyl ether, a dibutyl ether, methylethyl ether, a methyl propyl ether, a methyl butyl ether, or anycombination thereof; tetrahydrofuran, a dihydrofuran, 1,3-dioxolane,tetrahydropyran, a dihydropyran, a pyran, a dioxane, or any combinationthereof; furan, benzofuran, isobenzofuran, isobenzofuran, dibenzofuran,or any combination thereof; diphenyl ether, a ditolyl ether, or anycombination thereof; alternatively, dimethyl ether; alternatively,diethyl ether; alternatively, a dipropyl ether; alternatively, a dibutylether; alternatively, methyl ethyl ether; alternatively, a methyl propylether; alternatively, a methyl butyl ether; alternatively,tetrahydrofuran; alternatively, a dihydrofuran; alternatively,1,3-dioxolane; alternatively, tetrahydropyran; alternatively, adihydropyran; alternatively, a pyran; alternatively, a dioxane;alternatively, furan; alternatively, benzofuran; alternatively,isobenzofuran; alternatively, isobenzofuran; alternatively,dibenzofuran; alternatively, diphenyl ether; or alternatively, a ditolylether.

In an embodiment, each amine which can be utilized as the non-pyridinebisimine neutral ligand independently can be a monohydrocarbylamine, adihydrocarbylamine, or a trihydrocarbylamine, or any combinationthereof; alternatively, monohydrocarbylamine; alternatively, adihydrocarbylamine; or alternatively, a trihydrocarbylamine.Monohydrocarbylamines which can be utilized as the non-pyridine bisimineneutral ligand can be a C₁ to C₃₀, a C₁ to C₂₀, a C₁ to C₁₀, or a C₁ toC₅ monohydrocarbylamine. Dihydrocarbylamines which can be utilized asthe non-pyridine bisimine neutral ligand can be a C₂ to C₃₀, a C₂ toC₂₀, a C₂ to C₁₀, or a C₂ to C₅ dihydrocarbylamine. Trihydrocarbylamineswhich can be utilized as the non-pyridine bisimine neutral ligand can bea C₃ to C₃₀, a C₃ to C₂₀, or a C₃ to C₁₀ dihydrocarbylamine. Hydrocarbylgroups (general and specific) are disclosed herein (e.g., as substituentgroups, among other places) and can be utilized without limitation tofurther describe the monohydrocarbylamines, dihydrocarbylamines, and/ortrihydrocarbylamines which can be utilized as the non-pyridine bisimineneutral ligand. Generally, each hydrocarbyl group of thedihydrocarbylamine (or trihydrocarbylamine) is independent of each otherand can be the same: or alternatively, can be different. In anon-limiting embodiment, the monohydrocarbylamine, which can be utilizedas the non-pyridine bisimine neutral ligand can be, comprise, or consistessentially of, methyl amine, ethyl amine, propyl amine, butyl amine, orany combination thereof; alternatively, methyl amine; alternatively,ethyl amine; alternatively, propyl amine; or alternatively, butyl amine.In some embodiments, the dihydrocarbylamine, which can be utilized asthe non-pyridine bisimine neutral ligand can be, comprise, or consistessentially of, dimethyl amine, diethyl amine, dipropyl amine,dibutylamine, or any combination thereof; alternatively, dimethyl amine;alternatively, diethyl amine; alternatively, dipropyl amine; oralternatively, dibutylamine. In some embodiments, thetrihydrocarbylamine, which can be utilized as the non-pyridine bisimineneutral ligand can be, comprise, or consist essentially of, trimethylamine, triethyl amine, tripropyl amine, tributyl amine, or anycombination thereof; alternatively, trimethyl amine; alternatively,triethyl amine; alternatively, tripropyl amine; or alternatively,tributyl amine.

In an embodiment, the organoaluminum compound which can be utilized inthe processes described herein can comprise an aluminoxane, analkylaluminum compound, or a combination thereof; alternatively, analuminoxane; or alternatively, an alkylaluminum compound. In anembodiment, the alkylaluminum compound can be a trialkylaluminum, analkylaluminum halide, an alkylaluminum alkoxide, or any combinationthereof. In some embodiments, the alkylaluminum compound can be atrialkylaluminum, an alkylaluminum halide, or any combination thereof;alternatively, a trialkylaluminum, an alkylaluminum halide, or anycombination thereof; or alternatively, a trialkylaluminum. In otherembodiments, the alkylaluminum compound can be a trialkylaluminum;alternatively, an alkylaluminum halide; or alternatively, analkylaluminum alkoxide.

In an aspect, each alkyl group of any organoaluminum compound or anyalkylaluminum compound disclosed herein (e.g., trialkylaluminum,alkylaluminum halide, alkylaluminum alkoxide or aluminoxane)independently can be a C₁ to C₂₀, a C₁ to C₁₀, or a C₁ to C₆ alkylgroup. In an embodiment, each alkyl group of any organoaluminum compoundor any alkylaluminum compound disclosed herein (e.g., trialkylaluminum,alkylaluminum halide, alkylaluminum alkoxide, or aluminoxane)independently can be a methyl group, an ethyl group, a propyl group, abutyl group, a pentyl group, a hexyl group, a heptyl group, or an octylgroup; alternatively, a methyl group, a ethyl group, a butyl group, ahexyl group, or an octyl group. In some embodiments, each alkyl group ofany organoaluminum compound or any alkylaluminum compound disclosedherein (e.g., trialkylaluminum, alkylaluminum halide, alkylaluminumalkoxide, or aluminoxane) independently can be a methyl group, an ethylgroup, an n-propyl group, an n-butyl group, an iso-butyl group, ann-hexyl group, or an n-octyl group; alternatively, a methyl group, anethyl group, an n-butyl group, or an iso-butyl group; alternatively, amethyl group; alternatively, an ethyl group; alternatively, an n-propylgroup; alternatively, an n-butyl group; alternatively, an iso-butylgroup; alternatively, an n-hexyl group; or alternatively, an n-octylgroup.

In an aspect, each halide of any alkylaluminum halide disclosed hereinindependently can be chloride, bromide, or iodide. In some embodiments,each halide of any alkylaluminum halide disclosed herein can be chlorideor bromide; or alternatively, or chloride.

In an aspect, each alkoxide group of any alkylaluminum alkoxidedisclosed herein independently can be a C₁ to C₂₀, a C₁ to C₁₀, or a C₁to C₆ alkoxy group. In an embodiment, each alkoxide group of anyalkylaluminum alkoxide disclosed herein independently can be a methoxygroup, an ethoxy group, a propoxy group, a butoxy group, a pentoxygroup, a hexoxy group, a heptoxy group, or an octoxy group;alternatively, a methoxy group, a ethoxy group, a butoxy group, a hexoxygroup, or an octoxy group. In some embodiments, each alkoxide group ofany alkylaluminum alkoxide disclosed herein independently can be amethoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group,an iso-butoxy group, an n-hexoxy group, or an n-octoxy group;alternatively, a methoxy group, an ethoxy group, an n-butoxy group, oran iso-butoxy group; alternatively, a methoxy group; alternatively, anethoxy group; alternatively, an n-propoxy group; alternatively, ann-butoxy group; alternatively, an iso-butoxy group; alternatively, ann-hexoxy group; or alternatively, an n-octoxy group.

In a non-limiting embodiment, the trialkylaluminum compound cancomprise, can consist essentially of, or can be, trimethylaluminum,triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum,trioctylaluminum, or mixtures thereof. In some non-limiting embodiments,the trialkylaluminum compound comprise, can consist essentially of, orcan be, trimethylaluminum, triethylaluminum, tripropylaluminum,tri-n-butylaluminum, tri-isobutylaluminum, trihexylaluminum,tri-n-octylaluminum, or mixtures thereof, alternatively,triethylaluminum, tri-n-butylaluminum, tri-isobutylaluminum,trihexylaluminum, tri-n-octylaluminum, or mixtures thereof,alternatively, triethylaluminum, tri-n-butylaluminum, trihexylaluminum,tri-n-octylaluminum, or mixtures thereof. In other non-limitingembodiments, the trialkylaluminum compound can comprise, can consistessentially of, or can be, trimethylaluminum; alternatively,triethylaluminum; alternatively, tripropylaluminum; alternatively,tri-n-butylaluminum; alternatively, tri-isobutylaluminum; alternatively,trihexylaluminum; or alternatively, tri-n-octylaluminum.

In a non-limiting embodiment, the alkylaluminum halide can comprise, canconsist essentially of, or can be, diethylaluminum chloride,diethylaluminum bromide, ethylaluminum dichloride, ethylaluminumsesquichloride, and mixtures thereof. In some non-limiting embodiments,the alkylaluminum halide can comprise, can consist essentially of, orcan be diethylaluminum chloride, ethylaluminum dichloride, ethylaluminumsesquichloride, and mixtures thereof; or alternatively, diethylaluminumchloride; alternatively, diethylaluminum bromide; alternatively,ethylaluminum dichloride; or alternatively, ethylaluminumsesquichloride.

In a non-limiting embodiment, the aluminoxane can have a repeating unitcharacterized by the Formula I:

wherein R′ is a linear or branched alkyl group. Alkyl groups fororganoaluminum compounds are independently described herein and can beutilized without limitation to further describe the aluminoxanes havingFormula I. Generally, n of Formula I is greater than 1; oralternatively, greater than 2. In an embodiment, n can range from 2 to15; or alternatively, range from 3 to 10.

In a non-limiting embodiment, the aluminoxane can comprise, can consistessentially of, or can be, methylaluminoxane (MAO), ethylaluminoxane,modified methylaluminoxane (MMAO), n-propylaluminoxane,iso-propyl-aluminoxane, n-butylaluminoxane, sec-butylaluminoxane,iso-butylaluminoxane, t-butylaluminoxane, 1-pentyl-aluminoxane,2-entylaluminoxane, 3-pentyl-aluminoxane, iso-pentyl-aluminoxane,neopentylaluminoxane, or mixtures thereof. In some non-limitingembodiments, the aluminoxane can comprise, can consist essentially of,or can be, methylaluminoxane (MAO), modified methylaluminoxane (MMAO),isobutyl aluminoxane, t-butyl aluminoxane, or mixtures thereof. In othernon-limiting embodiments, the aluminoxane can be, comprise, or consistessentially of, methylaluminoxane (MAO); alternatively,ethylaluminoxane; alternatively, modified methylaluminoxane (MMAO);alternatively, n-propylaluminoxane; alternatively,iso-propyl-aluminoxane; alternatively, n-butylaluminoxane;alternatively, sec-butylaluminoxane; alternatively,iso-butylaluminoxane; alternatively, t-butyl aluminoxane; alternatively,1-pentyl-aluminoxane; alternatively, 2-pentylaluminoxane; alternatively,3-pentyl-aluminoxane; alternatively, iso-pentyl-aluminoxane; oralternatively, neopentylaluminoxane.

In an aspect, the processes described herein can utilize an organicreaction medium. Generally, the organic reaction medium can act as asolvent and/or a diluent in the processes described herein. In anembodiment, the organic reaction medium can comprise, can consistessentially of, or can be, a, at least one, or one or more,hydrocarbon(s); or alternatively, an, at least one, or one or more,aliphatic hydrocarbon(s). In some embodiments, the organic reactionmedium can comprise, can consist essentially of, or can be, a saturatedaliphatic hydrocarbon, an olefinic aliphatic hydrocarbon, or anycombination thereof; alternatively, a, at least one, or one or more,saturated aliphatic hydrocarbon(s); or alternatively, an, at least one,or one or more, olefinic aliphatic hydrocarbon(s). General and specifichydrocarbons, aliphatic hydrocarbons, saturated aliphatic hydrocarbons,and olefinic aliphatic hydrocarbons are described herein and can beutilized without limitation as the organic reaction medium.

In an embodiment, the hydrocarbon, aliphatic hydrocarbon, saturatedaliphatic hydrocarbon, or olefinic aliphatic hydrocarbon which can beutilized as the organic reaction medium can comprise, can consistessentially of, or can be, a, at least one, or one or more, C₈ to C₁₈, aC₈ to C₁₆, or a C₁₀ to C₁₄ hydrocarbon(s), aliphatic hydrocarbon,saturated aliphatic hydrocarbon, or olefinic aliphatic hydrocarbon. The,the at least one, or the one or more, hydrocarbon(s), aliphatichydrocarbon(s), saturated aliphatic hydrocarbon(s), or olefinicaliphatic hydrocarbon(s) can be cyclic or acyclic and/or can be linearor branched, unless otherwise specified. In some embodiments, thesaturated aliphatic hydrocarbon which can be utilized as the organicreaction medium can be, comprise, or consist essentially of, octane(s),decane(s), dodecane(s), tetradecane(s), hexadecane(s), octadecane(s), orany combination thereof; alternatively, decane(s), dodecane(s),tetradecane(s), or any combination thereof; alternatively, octane(s);alternatively, decane(s); alternatively, dodecane(s); alternatively,tetradecane(s) alternatively, hexadecane(s) or alternatively,octadecane(s). In an embodiment, the specific carbon numbered saturatedaliphatic hydrocarbon which can be utilized as the organic reactionmedium can comprise, can consist essentially of, or can be, a, at leastone, or one or more, specific carbon numbered saturated aliphatichydrocarbon(s). In an embodiment, the olefinic aliphatic hydrocarbonwhich can be utilized as the organic reaction medium can comprise, canconsist essentially of, or can be, a, at least one, or one or more, C₈to C₁₈, C₈ to C₁₆, or C₁₀ to C₁₄ olefinic aliphatic hydrocarbon. In someembodiments, the olefinic aliphatic hydrocarbon which can be utilized asthe organic reaction medium can comprise, can consist essentially of, orcan be, an, at least one, or one or more, alpha olefin(s); oralternatively, a, at least one, or one or more, normal alpha olefin(s).In a non-limiting embodiment, the olefinic aliphatic hydrocarbon whichcan be utilized as the organic reaction medium can be, comprise, orconsist essentially of, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,1-hexadecene, 1-octadecene, or any combination thereof; alternatively,1-decene, 1-dodecene, 1-tetradecene, or any combination thereof;alternatively, 1-decene; alternatively, 1-dodecene; or alternatively,1-tetradecene. In an aspect the organic reaction medium can besubstantially devoid of a halogenated compound. As utilized herein, anorganic reaction medium substantially devoid of halogenated compoundsmeans that the organic reaction medium can contain less than 1 wt. %,0.9 wt. %, 0.8 wt. %, 0.7 wt. %, 0.6 wt. %, 0.5 wt. %, 0.4 wt. %, 0.3wt. %, 0.2 wt. %, 0.1 wt. %, 0.05 wt. %, or 0.0 wt. 1% halogenatedcompounds based upon the weight of the organic reaction medium.

In an aspect, the oligomer product can be formed in a reaction zone. Inan embodiment, the reaction zone of any process described herein cancomprise a continuous stirred tank reactor, a plug flow reactor, or anycombination thereof; alternatively, a continuous stirred tank reactor;or alternatively, a plug flow reactor. In an embodiment, the reactionzone of any process described herein can comprise a continuous stirredtank reactor, a loop reactor, a solution reactor, a tubular reactor, arecycle reactor, a bubble reactor, or any combination thereof;alternatively, a continuous stirred tank reactor; alternatively, a loopreactor; alternatively, a solution reactor; alternatively, a tubularreactor; alternatively, a recycle reactor; or alternatively, a bubblereactor. In some embodiments, the reaction zone in which the oligomerproduct can be formed can comprise multiple reactors; or alternatively,only one reactor. When multiple reactors are present, each of thereactors can be the same or can be different types of reactors.Additionally, when reaction zone can comprise more than one reactor,each reactor independently can be any reactor described herein, and thereactors can be arranged in series, parallel, or any combinationthereof; alternatively, in series; or alternatively, in parallel.

It should be noted that when the reaction zone can comprise multiplereactors, each reactor can be independent of each other (regardless ofwhether they are operated in series or parallel). As such, the contactmodes (if needed), the conditions under which the oligomer product canbe formed, the oligomer product formation parameters under which theoligomer product can be formed and/or the reaction zone conditions canbe different for each reactor. In particular, when reaction zonecomprises multiple reactors in series, each reactor can be operated toachieve different goals. For example, a first reactor can be operated toi) contact of the ethylene and one or more the pyridine bisimine ironsalt complex, the alkylaluminum compound, and the organic reactionmedium, ii) initiate production of the oligomer product under a firstset of conditions capable of producing the oligomer product to someintermediate ethylene conversion and the effluent of the first reactortransferred to a second reactor operated to achieve the desired ethyleneconversion under a second set of conditions capable of producing theoligomer product (with or without additional ethylene and one or morethe pyridine bisimine iron salt complex, the alkylaluminum compound, andthe organic reaction medium being added to the reactor/reaction zone).

In any aspect or embodiment, the oligomer product can be formed at, thereaction zone can have, or the reaction zone can operate at, conditionsthat can comprise, either singly or in any combination, an iron of theiron salt concentration or iron of the pyridine bisimine iron saltcomplex concentration, a pyridine bisimine to iron salt equivalent ratiocharged to the reaction zone (depending upon the catalyst systemutilized), aluminum of the organoaluminum compound to the iron of theiron salt molar ratio or iron of the pyridine bisimine iron salt complexmolar ratio (depending upon the catalyst system utilized), aluminum ofthe organoaluminum compound concentration, an ethylene partial pressure,an ethylene to organic reaction medium mass ratio, a temperature (or anaverage temperature), a Schultz-Flory K value, a hydrogen partialpressure, or a hydrogen to ethylene mass ratio. In an embodiment, theoligomer product can be formed at, the reaction zone can have, or thereaction zone can operate at, conditions that can comprise, eithersingly or in any combination, an iron of the iron salt or iron of thepyridine bisimine iron salt complex concentration (depending upon thecatalyst system utilized), aluminum of the organoaluminum compound tothe iron of the iron salt or iron of the pyridine bisimine iron saltcomplex molar ratio (depending upon the catalyst system utilized), anethylene partial pressure, and an ethylene to organic reaction mediummass ratio; or alternatively, an iron of the iron salt or iron of thepyridine bisimine iron salt complex concentration (depending upon thecatalyst system utilized), aluminum of the organoaluminum compound tothe iron of the iron salt or iron of the pyridine bisimine iron saltcomplex molar ratio (depending upon the catalyst system utilized), anethylene partial pressure, an ethylene to organic reaction medium massratio, and optionally a hydrogen partial pressure or hydrogen toethylene mass ratio. In another embodiment, the oligomer product can beformed at, the reaction zone can have, or the reaction zone can operateat, conditions that can comprise, either singly or in any combination aniron of the iron salt or iron of the pyridine bisimine iron salt complexconcentration (depending upon the catalyst system utilized);alternatively, a pyridine bisimine to iron salt equivalent ratio chargedto the reaction zone; alternatively, aluminum of the organoaluminumcompound to the iron of the iron salt or iron of the pyridine bisimineiron salt complex molar ratio(depending upon the catalyst systemutilized); alternatively, aluminum of the organoaluminum compoundconcentration; alternatively, an ethylene partial pressure;alternatively, an ethylene to organic reaction medium mass ratio;alternatively, a temperature (or an average temperature); alternatively,a Schultz-Flory K value; alternatively, hydrogen partial pressure; oralternatively, a hydrogen to ethylene mass ratio.

In any aspect and/or embodiment, the oligomer product can be formed at,the reaction zone can have, or the reaction zone can operate at, aminimum iron of the iron salt or iron of the pyridine bisimine iron saltcomplex concentration (hereafter iron concentration or Fe concentration)of 5×10⁻⁴ mmol Fe/kg, 7×10⁻⁴ mmol Fe/kg, or 9×10⁻⁴ mmol Fe/kg;alternatively or additionally, a maximum reaction zone iron of the ironsalt or iron of the pyridine bisimine iron salt complex concentration of5×10⁻³ mmol Fe/kg, 4×10⁻³ mmol Fe/kg, or 3×10⁻³ mmol Fe/kg. In anembodiment, the oligomer product can be formed at, the reaction zone canhave, or the reaction zone can operate at, an iron concentration in therange of any minimum iron concentration disclosed herein to any maximumiron concentration disclosed herein. In a non-limiting embodiment, theoligomer product can be formed at, the reaction zone can have, or thereaction zone can operate at, an iron concentration in the range of5×10⁻⁴ mmol Fe/kg to 5×10⁻³ mmol Fe/kg, 7×10⁻⁴ mmol Fe/kg to 7×10⁻³ mmolFe/kg, or 9×10⁻⁴ mmol Fe/kg to 3×10⁻³ mmol Fe/kg. Other ironconcentration ranges that can be utilized are readily apparent to thoseskilled in the art with the aid of this disclosure. As utilized hereinthe phrases “iron of the iron salt concentration” and “iron of thepyridine bisimine iron salt complex concentration” refer to the ironconcentration within a solution, stream, or vessel (e.g., reaction zone)that is attributable to the iron of the iron salt or the iron of thepyridine bisimine iron salt complex, respectively.

In any aspect and/or embodiment, the oligomer product can be formed at,the reaction zone can have, or the reaction zone can operate at, aminimum pyridine bisimine to iron salt equivalent ratio charged to thereaction zone (also referred to as a minimum pyridine bisimine to ironsalt equivalent ratio) of 0.8:1, 0.9:1, or 0.95:1; alternatively oradditionally, a maximum pyridine bisimine to iron salt equivalent ratioequivalent ratio charged to the reaction zone (also referred to as amaximum pyridine bisimine to iron salt equivalent ratio) of 1.2:1, 1.15,1.1:1, or 1.05:1. In an embodiment, the oligomer product can be formedat, the reaction zone can have, or the reaction zone can operate at, apyridine bisimine to iron salt equivalent ratio charged to the reactionzone (hereafter, a pyridine bisimine to iron salt equivalent ratio) inthe range of maximum pyridine bisimine to iron salt equivalent ratiodisclosed herein to any maximum pyridine bisimine to iron saltequivalent ratio disclosed herein. In a non-limiting embodiment, thepyridine bisimine to iron salt equivalent ratio can be in the range of0.8:1 to 5:1, from 0.9:1 to 4:1, from 0.90:1 to 3:1, from 0.95:1 to 3:1,or from 0.95:1 to 2.5:1. Other pyridine bisimine to iron salt equivalentratio ranges that can be utilized are readily apparent to those skilledin the art with the aid of this disclosure.

In any aspect and/or embodiment, the oligomer product can be formed at,the reaction zone can have, or the reaction zone can operate at, aminimum reaction zone aluminum of the organoaluminum compound to theiron of the iron salt or pyridine bisimine iron salt complex molar ratio(also referred to as minimum aluminum:iron or Al:Fe molar ratio) of300:1, 350:1, or 400:1; alternatively or additionally, a maximumreaction zone iron of the iron salt or iron of the pyridine bisimineiron salt complex concentration (also referred to as maximumaluminum:iron or Al:Fe molar ratio) of 800:1, 700:1, 600:1, or 500:1. Inan embodiment, the oligomer product can be formed, the reaction zone canhave, or the reaction zone can operate, at an aluminum:iron molar ratioin the range of any minimum iron of the iron salt or iron of thepyridine bisimine iron salt complex concentration disclosed herein toany maximum iron of the iron salt or iron of the pyridine bisimine ironsalt complex concentration disclosed herein. In a non-limitingembodiment, the oligomer product can be formed, the reaction zone canhave, or the reaction zone can operate, at an aluminum to iron molarratio (also referred to as aluminum:iron or Al:Fe molar ratio) in therange of 300:1 to 800:1, 350:1 to 700:1, 350:1 to 600:1, 350:1 to 500:1,400:1 to 600:1, or 400:1 to 500:1. Other iron of the iron salt or ironof the pyridine bisimine iron salt complex concentration ranges that canbe utilized are readily apparent to those skilled in the art with theaid of this disclosure.

In any aspect and/or embodiment, the oligomer product can be formed at,the reaction zone can have, or the reaction zone can operate at, aminimum aluminum of the organoaluminum compound concentration (alsoreferred to as minimum aluminum concentration) of 0.75 mmol Al/kg, 0.9mmol Al/kg, or 1.1 mmol Al/kg; alternatively or additionally, a maximumaluminum concentration of the organoaluminum compound concentration(also referred to as maximum aluminum concentration) of 2.6 mmol Al/kg,2.2 mmol Al/kg, 1.8 mmol Al/kg, or 1.5 mmol Al/kg. In an embodiment, theoligomer product can be formed at, the reaction zone can have, or thereaction zone can operate at, an aluminum of the organoaluminum compoundconcentration also referred to as aluminum concentration) in the rangeof any minimum aluminum concentration disclosed herein to any maximumaluminum concentration disclosed herein. In a non-limiting embodiment,the oligomer product can be formed, the reaction zone can have, or thereaction zone can operate, at an aluminum concentration in the range of0.75 mmol Al/kg to 2.6 mmol Al/kg, 0.75 mmol Al/kg to 2.2 mmol Al/kg,0.9 mmol Al/kg to 1.8 mmol Al/kg, 1.1 mmol Al/kg to 1.8 mmol Al/kg, or1.1 mmol Al/kg to 1.5 mmol Al/kg. Other aluminum concentration rangesthat can be utilized are readily apparent to those skilled in the artwith the aid of this disclosure. As utilized herein the phrase “aluminumof the organoaluminum compound concentration” refers to the aluminumconcentration within a solution, stream, or vessel (e.g., reaction zone)that is attributable to the aluminum of the organoaluminum compound.

In any aspect and/or embodiment, the oligomer product can be formed at,the reaction zone can have, or the reaction zone can operate at, aminimum ethylene partial pressure of 750 psi (5.17 MPa), 775 psi (5.34kPa), or 800 psi (5.52 kPa); alternatively or additionally, a maximumethylene partial pressure of 1,200 psi (8.27 MPa), 1,100 psi (7.58 MPa),or 1000 psi (6.89 MPa). In an embodiment, the oligomer product can beformed at, the reaction zone can have, or the reaction zone can operateat, an ethylene partial pressure in the range of any minimum ethylenepartial pressure disclosed herein to any maximum ethylene partialpressure disclosed herein. In some non-limiting embodiments, theoligomer product can be formed at, the reaction zone can have, or thereaction zone can operate at, an ethylene partial pressure in the rangeof 750 psi (5.17 MPa) to 1,200 psi (8.27 MPa), from 775 psi (5.34 kPa)to 1,100 psi (7.58 MPa), or from 800 psi (5.52 kPa) to 1000 psi (6.89MPa). Other ethylene partial pressure ranges are readily apparent tothose skilled in the art with the aid of this disclosure.

In any aspect and/or embodiment, the oligomer product can be formed at,the reaction zone can have, or the reaction zone can operate at, aminimum ethylene:organic reaction medium mass ratio of 0.8:1, 1:1,1.25:1, or 1.5:1; alternatively, or additionally, a maximumethylene:organic reaction medium mass ratio of 4.5:1, 4:1, 3.5:1, 3:1,or 2.5:1. In an embodiment, the oligomer product can be formed at, thereaction zone can have, or the reaction zone can operate at, anethylene:organic reaction medium mass ratio in the range of any minimumethylene:organic reaction medium mass ratio disclosed herein to anymaximum ethylene:organic reaction medium mass ratio disclosed herein. Insome non-limiting embodiments, the oligomer product can be formed at,the reaction zone can have, or the reaction zone can operate at, anethylene:organic reaction medium mass ratio in the range of 0.8:1 to4.5:1, 1:1 to 4:1, 1:1 to 3.5:1, 1.25:1 to 3:1, or 1.5:1 to 2.5:1. Otherethylene:organic reaction medium mass ratio ranges that can be utilizedare readily apparent to those skilled in the art with the aid of thisdisclosure.

In any aspect and/or embodiment, the oligomer product can be formed at,the reaction zone can have, or the reaction zone can operate at, aminimum reaction zone temperature of 75° C., 77° C., or 80° C.;alternatively or additionally, a maximum reaction zone reaction zonetemperature 95° C., 93° C., or 90° C. In an embodiment, the oligomerproduct can be formed at, the reaction zone can have, or the reactionzone can operate at, a reaction zone temperature in the range of anyminimum temperature disclosed herein to any maximum temperaturedisclosed herein. In a non-limiting embodiment, the oligomer product canbe formed at, the reaction zone can have, or the reaction zone canoperate at, a reaction zone temperature in the range of 75° C. to 95°C., 77° C. to 93° C., or 80° C. to 90° C. Other temperature ranges thatcan be utilized are readily apparent to those skilled in the art withthe aid of this disclosure. In embodiments where the temperature canvary within the reaction zone, the temperature provided herein canalternatively be an average temperature.

In any aspect and/or embodiment, the oligomer product can have a minimumSchultz-Flory K value of (or can be at least) 0.4, 0.45, 0.5; or, 0.55;alternatively or additionally, a maximum Schultz-Flory K value of 0.9,0.85, 0.8, 0.75, 0.7 or, 0.65. In an embodiment, the oligomer productcan have a Schultz-Flory K value in the range of any minimumSchultz-Flory K value disclosed herein to any maximum Schultz-Flory Kvalue disclosed herein. For example, in some non-limiting embodiments,the oligomer product can have a Schultz-Flory K value in the range from0.4 to 0.9; alternatively, from 0.4 to 0.8; alternatively, from 0.5 to0.8; alternatively, from 0.5 to 0.7; alternatively, from 0.55 to 0.7.Other oligomer product Schultz-Flory K value ranges are readily apparentfrom the present disclosure.

In any aspect and/or embodiment, the Schultz-Flory K value can bedetermined using any one or more of the C₈, C₁₀, C₁₂, C₁₄, or C₁₆oligomer products. In an embodiment, the Schultz-Flory K value can be anaverage of any two or more Schultz-Flory K values using differentadjacent pairs of produced oligomers described herein. In someembodiments, the Schultz-Flory K value can be an average of any twoSchultz-Flory K values described herein; alternatively, any threeSchultz-Flory K values described herein; or alternatively, any fourSchultz-Flory K values described herein. For example, the Schultz-FloryK value can be determined using the C₈ and C₁₀ oligomer product;alternatively, the C₁₀ and C₁₂ oligomer product; alternatively, the C₁₂and C₁₄ oligomer product; alternatively, the C₁₄ and C₁₆ oligomerproduct; alternatively, the C₈, C₁₀, and C₁₂ oligomer product.

In any aspect and/or embodiment wherein hydrogen is utilized, theoligomer product can be formed (or the reaction zone can operate) at aminimum hydrogen partial pressure of 1 psi (6.9 kPa), 2 psi (14 kPa); 5psi (34 kPa), 10 psi (69 kPa), or 15 psi (103 kPa); alternatively oradditionally a maximum hydrogen partial pressure of 200 psi (1.4 MPa),150 psi (1.03 MPa), 100 psi (689 kPa), 75 psig (517 kPa), or 50 psi (345kPa). In an embodiment, the oligomer product can be formed (or thereaction zone can operate) at a hydrogen partial pressure in the rangeof any minimum hydrogen partial pressure disclosed herein to any maximumhydrogen partial pressure disclosed herein. In some non-limitingembodiments wherein hydrogen is utilized, the oligomer product can beformed (or the reaction zone can operate) at a hydrogen partial pressurefrom 1 psi (6.9 kPa) to 200 psi (1.4 MPa), from 5 psi (34 kPa) to 150psi (1.03 MPa), from 10 psi (69 kPa) to 100 psi (689 kPa), or from 15psi (100 kPa) to 75 psig (517 kPa). Other hydrogen partial pressureranges that can be utilized are readily apparent to those skilled in theart with the aid of this disclosure.

In any aspect and/or embodiment wherein hydrogen is utilized, theoligomer product can be formed (or the reaction zone can operate) at aminimum hydrogen to ethylene mass ratio of (0.05 g hydrogen)/(kgethylene), (0.1 g hydrogen)/(kg ethylene), (0.25 g hydrogen)/(kgethylene), (0.4 g hydrogen)/(kg ethylene), or (0.5 g hydrogen)/(kgethylene); alternatively or additionally, at a maximum hydrogen toethylene mass ratio can be (5 g hydrogen)/(kg ethylene), (3 ghydrogen)/(kg ethylene), (2.5 g hydrogen)/(kg ethylene), (2 ghydrogen)/(kg ethylene), or (1.5 g hydrogen)/(kg ethylene). In anembodiment, the oligomer product can be formed (or the reaction zone canoperate) at a hydrogen to ethylene mass ratio in the range of anyminimum hydrogen to ethylene mass ratio disclosed herein to any maximumhydrogen to ethylene mass ratio disclosed herein. In some non-limitingembodiments, the oligomer product can be formed (or the reaction zonecan operate) at a hydrogen to ethylene mass ratio from (0.05 ghydrogen)/(kg ethylene) to (5 g hydrogen)/(kg ethylene), from (0.25 ghydrogen)/(kg ethylene) to (5 g hydrogen)/(kg ethylene), from (0.25 ghydrogen)/(kg ethylene) to (4 g hydrogen)/(kg ethylene), from (0.4 ghydrogen)/(kg ethylene) to (3 g hydrogen)/(kg ethylene), from (0.4 ghydrogen)/(kg ethylene) to (2.5 g hydrogen)/(kg ethylene), from (0.4 ghydrogen)/(kg ethylene) to (2 g hydrogen)/(kg ethylene), or from (0.5 ghydrogen)/(kg ethylene) to (2 g hydrogen)/(kg ethylene). Other hydrogento ethylene mass ratio ranges that can be utilized are readily apparentto those skilled in the art with the aid of this disclosure.

In any aspect and/or embodiment, the processes described herein canproduce an oligomer product with high selectivity to linear alphaolefins; or alternatively, to normal alpha olefins. In some embodiments,the processes described herein can produce a reactor effluent whereinthe C₆ olefin oligomer product has a 1-hexene content of at least 98.5wt. %; alternatively, at least 98.75 wt. %; alternatively, at least 99.0wt. %; or alternatively, at least 99.25 wt. %. In other embodiments, theprocesses described herein can produce a reactor effluent wherein the C₈olefin oligomer product has a 1-octene content of at least 98 wt. %;alternatively, at least 98.25 wt. %; alternatively, at least 98.5 wt. %;alternatively, at least 98.75 wt. %; or alternatively, at least 99.0 wt.%. In yet other embodiments, the processes described herein can producea reactor effluent wherein the C₁₀ olefin oligomer product has a1-decene content of at least 97.5 wt. %; alternatively, at least 97.75wt. %; alternatively, at least 98 wt. %; alternatively, at least 98.25wt. %; or alternatively, at least 98.5 wt. %. In yet other embodiments,the processes described herein can produce a reactor effluent whereinthe C₁₂ olefin oligomer product has a 1-dodecene content of at least96.5 wt. %; alternatively, at least 97 wt. %; alternatively, at least97.5 wt. %; alternatively, at least 97.75 wt. %; or alternatively, atleast 98.0 wt. %. In yet other embodiments, the processes describedherein can produce a reactor effluent wherein the oligomer product cancomprise any combination of any C₆ olefin oligomer product 1-hexenecontent described herein, any C₈ olefin oligomer product 1-octenecontent described herein, any C₁₀ olefin oligomer product 1-decenecontent described herein, and/or any C₈ olefin oligomer product 1-octenecontent described herein. In some non-limiting examples, the processesdescribed herein can produce a reactor effluent having a C₆ olefinoligomer product 1-hexene content of at least 99 wt. % and a C₁₂ olefinoligomer product 1-dodecene content of at least 97.5 wt. %;alternatively, a C₈ olefin oligomer product 1-octene content of at least98.5 wt. % and a C₁₂ olefin oligomer product 1-dodecene octene contentof at least 97.5 wt. %; or alternatively, a C₆ olefin oligomer product1-hexene content of at least 99 wt. %, a C₈ olefin oligomer product1-octene content of at least 98.5 wt. %, a C₁₀ olefin oligomer product1-decene content of at least 98 wt. %, and a C₁₂ olefin oligomer product1-dodecene content of at least 97.5 wt. %. Other combinations of reactoreffluent olefin oligomer 1-alkene contents are readily apparent from thepresent disclosure.

Without being limited to theory, it is believed that various combinationof conditions at which the oligomer product can be formed, the reactionzone can have, or the reaction zone can operate, can lead to reducedreaction zone fouling though high molecular weight oligomer and/orpolymer adherence to the reaction zone surfaces. Polymer adherence tothe reaction zone surfaces such as heat transfer surfaces can reduce theability to control the temperature conditions at which the oligomerproduct can be formed, the reaction zone can have, or the reaction zonecan operate. In an aspect, the processes described herein can operatewhere the reaction zone (comprising a reactor) is online for a timeranging from any minimum online time disclosed herein to any maximumonline time disclosed herein. In an embodiment, the reaction zoneminimum online time can be at least 100 hours, 150 hours, 200 hours 300hours, 400 hours, 500 hours, or 600 hours. In an embodiment, thereaction zone maximum online time can be 9000 hours, 18000 hours, 27000hours, 36000 hours, or 45,000 hours. In a non-limiting embodiment, thereaction zone online time can range from 100 hours to 45,000 hours, 150hours to 36,000 hours, 200 hours to 36,000 hours, 300 hours to 36,000hours, 300 hours to 27,000 hours, 400 hours to 27,000 hours, 400 hoursto 18,000 hours, 500 hours to 27,000 hours, 500 hours to 18,000 hours,or 500 hours to 9,000 hours. Other reaction zone online time ranges arereadily apparent to those skilled in the art with the aid of thisdisclosure.

Without being limited to theory it is believed that various combinationof conditions at which the oligomer product can be formed, the reactionzone can have, or the reaction zone can operate, enable reduced reactionzone fouling though high molecular weight oligomer and/or polymeradherence to the reaction heat transfer surfaces (including reactor zonewalls) by reducing polymer swelling that can lead to polymer adhering toreaction zone surfaces (e.g., heat transfer surfaces, among othersurfaces). Without being limited there unto, it has been discovered thata particular combinations of reaction zone temperatures and organicreaction medium selections can reduce polymer swelling and lead toimproved process reaction zone operability (e.g., reaction zone onlinetime, among other potential reaction zone operability improvements). Insuch non-limiting embodiments, the processes disclosed herein can beoperated such that the oligomer product can be formed at, the reactionzone can have, or the reaction zone can operate at, a temperature withinany range of and including 75° C. to 95° C. disclosed herein and usingan organic reaction medium reaction medium comprising, or consistingessentially of any C₈ to C₁₈ aliphatic hydrocarbon (e.g., saturatedaliphatic hydrocarbon or olefinic aliphatic hydrocarbon) disclosedherein. In further embodiments, the processes can be operated such thatthe oligomer product can be formed at, the reaction zone can have, orthe reaction zone can operate at, conditions that can comprise, eithersingly or in any combination, any iron of the iron salt concentrationdisclosed herein or iron of the pyridine bisimine iron salt complexconcentration disclosed herein, any pyridine bisimine to iron saltequivalent ratio charged to the reaction zone disclosed herein, aluminumof the organoaluminum compound to the iron of the iron salt molar ratiodisclosed herein or iron of the pyridine bisimine iron salt complexmolar ratio disclosed herein, aluminum concentration disclosed herein,any ethylene partial pressure disclosed herein, any ethylene to organicreaction medium mass ratio disclosed herein, Schultz-Flory K valuedisclosed herein, any hydrogen partial pressure disclosed herein, or anyhydrogen to ethylene mass ratio disclosed herein.

In an aspect, the processes described herein can produce a reactoreffluent wherein the polymer component of the reaction zone effluentcomprises a maximum of 15 wt. % solids, alternatively a maximum of 10wt. % solids, alternatively a maximum of 8 wt. % solids. In annon-limiting alternative aspect, the processes described herein canproduce a reaction zone effluent wherein the polymer component of thereaction zone effluent comprises from 5 wt. % to 15 wt. % solids,alternatively from 7 wt. % to 12 wt. % solids, or alternatively from 7wt. % to 10 wt. % solids.

In an aspect, the processes described herein can produce a reactor zoneeffluent wherein the polymer component comprises greater than 90 wt. %,greater 92 wt. %, greater than 94 wt. %, greater than 96 wt. %, greaterthan 98 wt. %, or greater than 99 wt. % polymer having a molecularweight of less than 1000 g/mol.

In an aspect, the processes described herein can produce an oligomerproduct such that the less than 50 wt. %, 60 wt. % 70 wt. % or 75 wt. %of the oligomer product adhering to the reaction zone wall comprisespolyethylene has a M_(W) greater than 1000 g/mol.

Various aspect and/or embodiments described herein can refer tosubstituted groups or compound. In an embodiment, each substituent ofany aspect or embodiment calling for a substituent can be a halogen, ahydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen ora hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group;alternatively, a hydrocarbyl group or a hydrocarboxy group;alternatively, a halogen; alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. In an embodiment, each hydrocarbylsubstituent can be a C₁ to C₁₀, or a C₁ to C₅ hydrocarbyl group. In anembodiment, each hydrocarboxy group or substituent of any aspect orembodiment calling for a group substituent can be a C₁ to C₁₀, or a C₁to C₅ hydrocarboxy group. In an embodiment, any halide substituent ofany aspect or embodiment calling for a substituent can be a fluoride,chloride, bromide, or iodide; alternatively, a fluoride or chloride. Insome embodiments, any halide substituent of any aspect or embodimentcalling for a substituent can be a fluoride; alternatively, a chloride;alternatively, a bromide; or alternatively, an iodide.

In an embodiment, any hydrocarbyl substituent of any aspect and/orembodiment calling for a substituent can be an alkyl group, an arylgroup, or an aralkyl group; alternatively, an alkyl group;alternatively, an aryl group; or alternatively, an aralkyl group. In anembodiment, any alkyl substituent of any aspect and/or embodimentcalling for a substituent can be a methyl group, an ethyl group, ann-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group,an isobutyl group, a tert-butyl group, an n-pentyl group, a 2-pentylgroup, a 3-pentyl group, a 2-methyl-1-butyl group, a tert-pentyl group,a 3-methyl-1-butyl group, a 3-methyl-2-butyl group, or a neo-pentylgroup; alternatively, a methyl group, an ethyl group, an isopropylgroup, a tert-butyl group, or a neo-pentyl group; alternatively, amethyl group; alternatively, an ethyl group; alternatively, an isopropylgroup; alternatively, a tert-butyl group; or alternatively, a neo-pentylgroup. In an embodiment, any aryl substituent of any aspect and/orembodiment calling for a substituent can be phenyl group, a tolyl group,a xylyl group, or a 2,4,6-trimethylphenyl group; alternatively, a phenylgroup; alternatively, a tolyl group, alternatively, a xylyl group; oralternatively, a 2,4,6-trimethylphenyl group. In an embodiment, anyaralkyl substituent of any aspect or embodiment calling for asubstituent can be benzyl group or an ethylphenyl group(2-phenyleth-1-yl or 1-phenyleth-1-yl); alternatively, a benzyl group;alternatively, an ethylphenyl group; alternatively a 2-phenyleth-1-ylgroup; or alternatively, a 1-phenyleth-1-yl group.

In an embodiment, any hydrocarboxy substituent of any aspect and/orembodiment calling for a substituent can be an alkoxy group, an aryloxygroup, or an aralkoxy group; alternatively, an alkoxy group;alternatively, an aryloxy group, or an aralkoxy group. In an embodiment,any alkoxy substituent of any aspect and/or embodiment calling for asubstituent can be a methoxy group, an ethoxy group, an n-propoxy group,an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxygroup, a tert-butoxy group, an n-pentoxy group, a 2-pentoxy group, a3-pentoxy group, a 2-methyl-1-butoxy group, a tert-pentoxy group, a3-methyl-1-butoxy group, a 3-methyl-2-butoxy group, or a neo-pentoxygroup; alternatively, a methoxy group, an ethoxy group, an isopropoxygroup, a tert-butoxy group, or a neo-pentoxy group; alternatively, amethoxy group; alternatively, an ethoxy group; alternatively, anisopropoxy group; alternatively, a tert-butoxy group; or alternatively,a neo-pentoxy group. In an embodiment, any aryloxy substituent of anyaspect and/or embodiment calling for a substituent can be phenoxy group,a toloxy group, a xyloxy group, or a 2,4,6-trimethylphenoxy group;alternatively, a phenoxy group; alternatively, a toloxy group,alternatively, a xyloxy group; or alternatively, a2,4,6-trimethylphenoxy group. In an embodiment, any aralkoxy substituentof any aspect or embodiment calling for a substituent can be benzoxygroup.

For the purpose of any U.S. national stage filing from this application,all publications and patents mentioned in this disclosure areincorporated herein by reference in their entireties, for the purpose ofdescribing and disclosing the constructs and methodologies described inthose publications, which might be used in connection with the methodsof this disclosure. Any publications and patents discussed above andthroughout the text are provided solely for their disclosure prior tothe filing date of the present application. Nothing herein is to beconstrued as an admission that the inventors are not entitled toantedate such disclosure by virtue of prior invention.

In any application before the United States Patent and Trademark Office,the Abstract of this application is provided for the purpose ofsatisfying the requirements of 37 C.F.R. § 1.72 and the purpose statedin 37 C.F.R. § 1.72(b) “to enable the United States Patent and TrademarkOffice and the public generally to determine quickly from a cursoryinspection the nature and gist of the technical disclosure.” Therefore,the Abstract of this application is not intended to be used to construethe scope of the claims or to limit the scope of the subject matter thatis disclosed herein. Moreover, any headings that can be employed hereinare also not intended to be used to construe the scope of the claims orto limit the scope of the subject matter that is disclosed herein. Anyuse of the past tense to describe an example otherwise indicated asconstructive or prophetic is not intended to reflect that theconstructive or prophetic example has actually been carried out.

The present disclosure is further illustrated by the following examples,which are not to be construed in any way as imposing limitations uponthe scope thereof. On the contrary, it is to be clearly understood thatresort can be had to various other aspects, embodiments, modifications,and equivalents thereof which, after reading the description herein, cansuggest themselves to one of ordinary skill in the art without departingfrom the spirit of the present invention or the scope of the appendedclaims.

The data and descriptions provided in the following examples are givento show particular aspects and embodiments of the compounds, catalystsystems, and olefin oligomerization and/or olefin polymerization methodsdisclosed, and to demonstrate a number of the practices and advantagesthereof. The examples are given as a more detailed demonstration of someof the aspects and embodiments described herein and are not intended tolimit the disclosure or claims in any manner.

ADDITIONAL DISCLOSURE

The following enumerated aspects of the present disclosures are providedas non-limiting examples.

A first aspect which is a process comprising: A) continuouslyintroducing into a reaction zone i) ethylene, ii) a pyridine bisimineiron salt complex, iii) an organoaluminum compound, and iv) an organicreaction medium comprising, or consisting essentially of, one or more C₈to C₁₈ aliphatic hydrocarbons; and B) forming an oligomer product in thereaction zone, the reaction zone having an average temperature in arange of 75° C. to 95° C.

A second aspect which is a process comprising: A) continuouslyintroducing into a reaction zone i) ethylene, ii) an iron salt, iii) apyridine bisimine, iii) an organoaluminum compound, and iv) an organicreaction medium comprising, or consisting essentially of one or more C₈to C₁₈ aliphatic hydrocarbons; and B) forming an oligomer product in thereaction zone, the reaction zone having an average temperature in arange of 75° C. to 95° C.

A third aspect which is the process of the second aspect, wherein thereaction zone has an iron salt to pyridine bisimine equivalent ratio ina range of 0.8:1 to 1.2:1.

A fourth aspect which is a process of any one of the first through thethird aspects, wherein the reaction zone has an iron of the pyridinebisimine iron salt complex concentration of 5×10⁻⁴ mmol/kg to 5×10⁻³mmol/kg.

A fifth aspect which is the process of any one of the first through thefourth aspects, wherein the reaction zone has an aluminum of theorganoaluminum compound to iron of the pyridine bisimine iron saltcomplex molar ratio in a range of 300:1 to 800:1.

A sixth aspect which is the process of the fifth aspect, wherein thereaction zone aluminium of the organoaluminum compound to iron of theiron salt or iron of the pyridine bisimine iron salt complex molar ratioin a range of 300:1 to 500:1.

A seventh aspect which is the process of any one of the first throughthe sixth aspects, wherein the reaction zone has an ethylene partialpressure in a range of 750:1 psig to 1200 psig.

An eighth aspect which is the process of the seventh aspect, wherein thereaction zone ethylene partial pressure is in a range of 750 to 1000psi.

A ninth aspect which is the process of any one of the first through theeight aspects, wherein the reaction zone has an ethylene to organicreaction medium mass ratio of 0.8 to 4.5.

A tenth aspect which is the process of any one of the first through theninth aspects, wherein the reaction zone has an aluminum of theorganoaluminum compound concentration in a range of 0.75 mmol Al/kg to2.6 mmol Al/kg.

An eleventh aspect which is the process of any one of the first throughthe tenth aspects, wherein hydrogen is continuously introduced into thereaction zone and the reaction zone has a hydrogen partial pressure ofat least 5 psi.

A twelfth aspect which is a process comprising: A) continuouslyintroducing into a reaction zone i) ethylene, ii) an pyridine bisimineiron salt complex, iii) an organoaluminum compound, and iv) an organicreaction medium; B) forming an oligomer product in the reaction zone,the reaction zone having i) an iron of the pyridine bisimine iron saltcomplex concentration in a range of 5×10⁻⁴ mmol/kg to 5×10⁻³ mmol/kg,ii) an aluminum of the organo aluminum compound to iron of the pyridinebisimine iron salt complex molar ratio in a range of 300:1 to 800:1,iii) an ethylene partial pressure in a range of 750:1 psig to 1200 psig,iv) an ethylene to organic reaction medium mass ratio of 0.8 to 4.5, andv) an average temperature in a range of 75° C. to 95° C.; and optionallyvi) a hydrogen partial pressure of at least 5 psi.

A thirteenth aspect which is a process comprising: A) continuouslyintroducing into a reaction zone i) ethylene, ii) an iron salt, iii) apyridine bisimine, iv) an organoaluminum compound, and v) an organicreaction medium, and B) forming an oligomer product in the reactionzone, the reaction zone having i) an iron of the iron salt concentrationin a range of 5×10⁻⁴ mmol/kg to 5×10⁻³ mmol/kg, ii) an aluminum of theorgano aluminum compound to iron of the iron salt molar ratio in a rangeof 300:1 to 800:1, iii) an ethylene partial pressure in a range of 750psig to 1200 psig, iv) an ethylene to organic reaction medium mass ratioin a range of 0.8 to 4.5, v) a temperature in a range of 75° C. to 95°C., and optionally vi) a hydrogen partial pressure of at least 5 psi.

A fourteenth aspect which is the process of the thirteenth aspect,wherein the reaction zone has an iron salt to pyridine bisimineequivalent ratio in the range of 0.8:1 to 1.2:1.

A fifteenth aspect which is the process of any one of the twelfththrough the fourteenth aspects, wherein the reaction zone has analuminum of the organoaluminum compound concentration in a range of 0.75mmol Al/kg to 2.6 mmol Al/kg.

A sixteenth aspect which is the process of any one of the twelfththrough the fifteenth aspects, wherein the reaction zone aluminium ofthe organoaluminum compound to iron of the iron salt or iron of thepyridine bisimine iron salt complex molar ratio in the range of 300:1 to500:1.

A seventeenth aspect which is the process of any one of the twelfththrough the sixteenth aspects, wherein the reaction zone ethylenepartial pressure in the range of 750 to 1000 psi.

An eighteenth aspect which is the process of any one of the twelfththrough the seventeenth aspects, wherein the reaction zone ethylene toorganic reaction medium mass ratio in the range of 0.8:1 to 4.5:1.

A nineteenth aspect which is the process of any one of the twelfththrough the eighteenth aspects, wherein the organic reaction mediumcomprises, or consists essentially of, one or more aliphatichydrocarbons.

A twentieth aspect which is the process of the nineteenth aspects,wherein the organic reaction medium comprises, or consists essentiallyof, one or more C₈ to C₁₈ aliphatic hydrocarbons.

A twenty first aspect which is the process of any one of the firstthrough the eleventh aspects or the nineteenth aspect, wherein theorganic reaction medium comprises, or consists essentially of, one ormore C₈ to C₁₆ saturated aliphatic hydrocarbons.

A twenty second aspect which is the process of any one of the firstthrough the eleventh aspects or the nineteenth aspect, wherein theorganic reaction medium comprises, or consists essentially of, one ormore C₈ to C₁₆ olefinic aliphatic hydrocarbons.

A twenty third aspect which is the process of the twenty second aspect,wherein the organic reaction medium comprises, or consists essentiallyof, 1-decene, 1-dodecene, 1-tetradecene, or any combination thereof.

A twenty fourth aspect which is the process of any one of the firstthrough the twenty third aspects, wherein the organic reaction medium issubstantially devoid of a halogenated compound.

A twenty fifth aspect which is the process of any one of the firstthrough the twenty fourth aspects, wherein the reaction zone has atemperature in the range of 80° C. to 90° C.

A twenty sixth aspect which is the process of any one of the firstthrough the twenty fifth aspects, wherein the oligomer product formed inthe reaction zone has a Schultz-Flory K value in the range of 0.4 to 0.9(or in the range of 0.5 to 0.8).

A twenty seventh aspect which is the process of any one of the firstthrough the twenty sixth aspects, wherein greater than 50 wt. % of theoligomer product adhering to the reaction zone wall comprisespolyethylene having an M_(W) greater than 1000 g/mol.

A twenty eighth aspect which is the process of any one of the firstthrough the twenty seventh aspects, wherein the reaction zone is onlinefor at least 100 hours.

A twenty ninth aspect which is the process of any one of the firstthrough the twenty eighth aspects, further comprising continuouslydischarging a reaction zone effluent from the reaction zone.

A thirtieth aspect which is the process of any one of the first throughthe twenty ninth aspects, further comprising introducing the organicreaction medium to the reaction zone prior to introducing the iron saltpyridine bisimine complex, the iron salt, the pyridine bisiminecompound, or the ethylene to the reaction zone.

A thirty first aspect which is the process of any one of the firstthrough the thirtieth aspects, further comprising introducing 1) thepyridine bisimine iron salt complex, or 2) the iron salt, the pyridinebisimine to the reaction zone prior to introducing ethylene to thereaction zone.

A thirty second aspect which is the process of any one of the firstthrough the thirty first aspects, wherein the pyridine bisimine or thepyridine bisimine of the pyridine bisimine iron salt complex comprisesi) a 2,6-bis[(arylimine)hydrocarbyl]pyridine wherein the aryl groups canbe the same or different, ii) a bis[(substitutedarylimine)hydrocarbyl]pyridine, wherein the substituted aryl groups canbe the same or different, or iii) a[(arylimine)hydrocarbyl],[(substituted arylimine)hydrocarbyl]pyridine.

A thirty third aspect which is the process of the thirty second aspects,wherein 1) one, two, or three of the aryl groups and/or substituted arylgroups positions ortho to the carbon atom attached to the imine nitrogenindependently are a halogen, a primary carbon atom group, or a secondarycarbon atom group and the remainder of the aryl groups and/orsubstituted aryl groups positions ortho to the carbon atom attached tothe imine nitrogen are hydrogen, 2) one of the aryl groups and/orsubstituted aryl groups positions ortho to the carbon atom attached tothe imine nitrogen is a tertiary carbon atom group, none, one, or two ofthe aryl groups and/or substituted aryl groups positions ortho to thecarbon atom attached to the imine nitrogen independently are a halogen,a primary carbon atom group or a secondary carbon atom group, and theremainder of the aryl groups and/or substituted aryl groups positionsortho to the carbon atom attached to the imine nitrogen are hydrogen, 3)two of the aryl groups and/or substituted aryl groups positions ortho tothe carbon atom attached to the imine nitrogen independently are atertiary carbon atom group, none, or one of the aryl groups and/orsubstituted aryl groups positions ortho to the carbon atom attached tothe imine nitrogen independently are a halogen, a primary carbon atomgroup, or a secondary carbon atom group, and the remainder of the arylgroups and/or substituted aryl groups positions ortho to the carbon atomattached to the imine nitrogen are hydrogen, 4) one or two of the arylgroups and/or substituted aryl groups positions ortho to the carbon atomattached to the imine nitrogen independently are a tertiary carbon atomgroup(s) and the remainder of the aryl groups and/or substituted arylgroups positions ortho to the carbon atom attached to the imine nitrogenare hydrogen, 5) one or two of the aryl groups and/or substituted arylgroups positions ortho to the carbon atom attached to the imine nitrogenare a quaternary carbon atom group and the remainder of the aryl groupsand/or substituted aryl groups positions ortho to the carbon atomattached to the imine nitrogen are hydrogen, or 6) all four of thesubstituted aryl groups positions ortho to the carbon atom attached tothe imine nitrogen are fluorine.

A thirty fourth aspect which is the process of the thirty secondaspects, wherein the pyridine bisimine is selected from the groupconsisting of 2,6-bis[(phenylimine) methyl]pyridine,2,6-bis[(2-methylphenylimine)methyl]pyridine,2,6-bis[(2-ethylphenylimine)methyl]pyridine,2,6-bis[(2-isopropylphenylimine)methyl]pyridine,2,6-bis[(2,4-dimethylphenylimine)methyl]pyridine,2-[(2,4,6-trimethylphenylimine)methyl]-6-[(3,5-dimethylphenylimine)methyl]pyridine,and2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-t-butylphenylimine)methyl]pyridine.

A thirty-fifth aspect which is a process comprising A) continuouslyintroducing into a reaction zone i) ethylene, ii) an iron salt, iii) apyridine bisimine, iv) an organoaluminum compound, and v) an organicreaction medium comprising a C₈ to C₁₈ aliphatic hydrocarbon; and B)forming an oligomer product in the reaction zone, the reaction zonehaving an average temperature in a range of 75° C. to 95° C.

A thirty-sixth aspect which is a process comprising A) continuouslyintroducing into a reaction zone i) ethylene, ii) an pyridine bisimineiron salt complex, iii) an organoaluminum compound, and iv) an organicreaction medium comprising one or more C₈ to C₁₈ aliphatic hydrocarbons;and B) forming an oligomer product in the reaction zone, the reactionzone having an average temperature in a range of 75° C. to 95° C.

EXAMPLES

All manipulations were carried out using a nitrogen filled VacuumAtmospheres drybox and standard Schlenk techniques using oven driedglassware (>1 h at 110° C. under vacuum, −30 mmHg). Dichloromethane(DCM) was anhydrous grade from Fisher utilized in the drybox and storedover molecular sieves. Toluene was anhydrous grade from Sigma-Aldrichutilized in the drybox and stored over molecular sieves. Organicreaction mediums, cyclohexane and 1-dodecene, were obtained from ChevronPhillips Chemical Company, LP. The organic reaction mediums were thencharged to a N₂ degassed feed tanks (10 or 20 gal), further degassedwith N₂ and further purified using molecular sieves, activated alumina,and a reduced copper bed to remove water, oxygen/polar compounds, anddissolved oxygen. MMAO-3A (typically 6 to 8 wt. % aluminum) was obtainedfrom AkzoNobel Chemicals Company and stored in a N₂ filled drybox.Meta-xylene was obtained from Sigma-Aldrich, degassed under N₂ andstored over molecular sieves in the drybox. The pyridine bisimineligands(2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-t-butylphenylimine)methyl]pyridine,2-[(2,4,6-trimethylphenyl-imine)methyl]-6-[(4-methylphenylimine)methyl]pyridine,and2-[(2,4,6-trimethylphenylimine)methyl]-6-[(3,5-dimethylphenylimine)methyl]pyridine)and the pyridine bisimine iron complexes([2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-t-butylphenylimine)methyl]pyridine]FeCl₂)were prepared according to known procedures.

Ethylene oligomerizations were performed using the reaction systemillustrated in FIG. 1. The reaction system 200 had 1) a reaction zonecomprising a 500 mL autoclave reactor 10 l having a) an overheadmagnetic stirrer 20, b) an oil filled external jacket heating systemcontrolled an internal TI probe 30, c) separate feed lines for i)ethylene 45, ii) the pyridine bisimine and the iron salt, or thepyridine bisimine iron salt complex (PBFe) 55, and iii) anorganoaluminum compound (OAC) 65 and organic reaction medium (ORM) 75,d) an autoclave reactor effluent outlet line 85 (including a not shownreactor effluent sample port) heat traced to maintain a skin temperatureof 135° C., e) an organic reaction medium diluent feed tank 70, f) anorganic reaction medium feed pump 80 to provide the organic reactionmedium to the reaction zone though the an organoaluminum compound andorganic reaction medium inlet, g) an ISCO pump 105 coupled to anorganoaluminum compound charger 101 to feed the organoaluminum compoundto the suction side of the organic reaction medium feed pump, h) an ISCOpump 115 coupled to a charger 112 to feed the pyridine bisimine and ironsalt solution, or the pyridine bisimine iron salt complex solution tothe reaction zone through the pyridine bisimine and iron salt feed line,i) a regulated (0 to 600 g/hour) ethylene feed 120 to provide ethylenethrough the reaction zone ethylene feed inlet, j) a heat traced producttank 130 (to maintain an approximate temperature of 90° C.) to acceptreaction zone effluent from the reaction zone outlet line, k) a Badgerresearch control valve 140 (with the ability to maintain pressure from aminimum of 200 psig to a maximum of 1200 psig) on the product maintainpressure on the product tank and reaction zone, and 1) a nitrogen feedline 150 to maintain a nitrogen atmosphere on the reaction zone andproduct tank.

In a drybox, a clean dry 250 mL glass charging flask was washed withdesired solvent/diluent. The 250 mL glass charging flask was thendrained and charged with the desired quantity of the desired pyridinebisimine, the desired quantity of the desired iron salt, and desiredquantity of solvent/diluent (or the desired quantity of pyridinebisimine iron salt complex and the desired quantity of solvent/diluent).The 250 mL charging flask was then sealed and removed from the drybox.The contents of the 250 mL charging flask were then charged to thepyridine bisimine/iron salt solution (or pyridine bisimine iron saltcomplex solution) ISCO pump and the pyridine bisimine/iron salt solution(or pyridine bisimine iron salt complex solution) charge lines flushedwith approximately 15 mL of the pyridine bisimine/iron salt solution (orpyridine bisimine iron salt complex solution).

In a drybox, a clean dry 250 mL glass charging flask was washed withdesired solvent/diluent. The 250 mL glass charging flask was thendrained and charged with the desired quantity of nonane (used as aninternal standard) and desired amount of organoaluminum solution toachieve a 10:1 ratio, by volume, of nonane to the organoaluminumcompound solution. The desired quantity of organoaluminum compoundsolution. The 250 mL charging flask was then sealed and removed from thedrybox. The contents of the 250 mL charging flask were then charged tothe organoaluminum ISCO pump and the organoaluminum charge lines wereflushed with approximately 15 mL of the organoaluminum solution.

The 500 mL autoclave reactor was prepared for the ethyleneoligornerization using three cycles of filling the autoclave reactor to800 psig with dry nitrogen and then venting the autoclave reactor. Theproduct tank was then filed with dry nitrogen and brought to the desiredoperating temperature. A quick connect transfer line was then used toconnect the organic reaction medium feed tank to the autoclave reactor.The autoclave reactor was then filled with organic reaction medium usingnitrogen pressure. The quick connect transfer line was then disconnectedfrom the autoclave reactor. The organic reaction medium pump was thenstarted and the autoclave reactor was brought to the desiredoligomerization pressure. Once the oligomerization pressure wasachieved, the overhead magnetic stirrer was switched on and stirring setat a rate of approximately 1200 rpm. The external heating was theninitiated and the autoclave reactor was brought up to the desiredoligomerization temperature. The ISCO pumps for the organoaluminumcompound and the pyridine bisimine and iron salt solution (or thepyridine bisimine iron salt solution) were turned on and set to thedesired feed rates. Thirty minutes after initiating: the organoaluminumcompound feed and the pyridine bisimine and iron salt solution (or thepyridine bisimine iron salt solution) feed, ethylene was introduced tothe autoclave reactor at a rate of approximately 250 g/h. After onehour, the reaction zone effluent sample port was purged with reactoreffluent for a few minutes, a reaction effluent sample was taken,analyzed by low thermal mass gas chromatography (LTM-GC), and anestimate of catalyst system productivity determined. If the ethyleneconversion and catalyst system productivity was determined to be withinan acceptable range, the ethylene flow rate was then increased to thedesired flow rate by slowly increasing the ethylene flow rate at a rateof 100 g/hour. Reaction zone effluent samples were then taken every 30minutes by purging the reaction zone sample port for a few minutes andthen collecting a reaction zone effluent sample. The reaction zoneeffluent samples were then analyzed by LTM-GC using a 30 m Agilent DB1column operating with a flame ionization detector or a Agilent 6890 gaschromatographs using 50 m HP5 or DB5 column operating with a flameionization detector.

After completion of the oligomerization reaction, the pressure on theautoclave reactor was released and the liquids and solids from thereactor body and head were collected. The collected solids were dried,and weighed. The reactor solids were then reported as Rx Solids/kg NAOproduct.

The contents of the product tank were homogenized and then analyzed bytaking a 250 g of the product tank contents. The homogenized sample wassubject to rotary evaporation for one hour at 100° C. and −30 in Hg toeffectively remove the liquid. The mass of the remaining solids (wax andpolyethylene) was recorded and a portion of the solids was analyzed bythermogravimetric analysis (TGA). The quantity of the types of materialsin the solids sample was determined using the TGA temperature ranges ofA) liquids—<175° C., B) waxes—175° C. to 420° C., and C) polyethylene(PE)>420° C. The amount of polyethylene produced is then reported as %C₂H₄ to polyethylene.

Examples 1-14

Ethylene oligomerizations utilizing three different catalyst systemswere performed using the ethylene oligomerization procedure. Catalystsystem 1 comprised([2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-t-butylphenylimine)methyl]pyridine]FeCl₂)and MMAO-3A. Catalyst system 2 comprised2-[(2,4,6-trimethylphenylimine)methyl]-6-[(3,5-dimethylphenylimine)-methyl]pyridine),iron(III) acetylacetonate (hereafter Fe(acac)₃), and MMAO-3A. Catalystsystem 3 comprised2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-methylphenylimine)methyl]pyridine,iron(III) acetylacetonate (hereafter Fe(acac)₃), and MMAO-3A. Table 1provides information regarding the preparation of the iron compound andMMAO-3A solution utilized for the catalyst system in the ethyleneoligomerizations. Table 2 provides information regarding ethyleneoligomerization run conditions. Table 3 provides information regardingthe performance of the ethylene oligomerization.

TABLE 1 Ethylene Oligomerization Catalyst System Solution Data CatalystSystem Component Solution Concentrations Iron Compound Ligand MMAO-3ACatalyst Iron Compound Catalyst Concentration, Concentration,Concentration Exam. System Solvent Solvent Ratio mg/mL mg/mL mg/mL 1 1Dichloromethane — 0.25 — 72.3 2 1 Dichloromethane — 0.25 — 72.3 3 2Toluene — 0.047 0.078 72.3 4 2 Toluene — 0.047 0.078 72.3 5 2 m-xylene/103:47 0.047 0.078 72.3 Cyclohexane 6 2 m-xylene/ 103:47 0.047 0.07872.3 Cyclohexane 7 2 m-xylene/ 103:47 0.047 0.078 72.3 Cyclohexane 8 2m-xylene/ 103:47 0.047 0.078 72.3 Cyclohexane 9 2 Toluene/ 103:47 0.0470.078 72.3 Cyclohexane 10 2 Toluene — 0.047 0.078 72.3 11 2 m-xylene/103:47 0.047 0.078 72.3 Cyclohexane 12 2 m-xylene/ 103:47 0.047 0.07872.3 Cyclohexane 13 2 m-xylene/ 103:47 0.047 0.078 72.3 Cyclohexane 14 3m-xylene/ 103:47 0.047 0.078 72.3 Cyclohexane

TABLE 2 Ethylene Oligomerization Run Parameters Feed Rates MMAO- OrganicReactor Reactor Organic Iron 3A Reactor Fe Reactor Al Reaction Pressure,Temperature, Reaction, Compound Solution, Ethylene, concentration,concentration, Example Medium psig ° C. g/hour Solution, mL/h mL/hg/hour ppm by mass ppm by mass 1 cyclohexane 1000 100 350 3 5.4 300 0.134 2 1-dodecene 1000 100 450 3 7 425 0.1 33 3 1-dodecene 1000 100 5009.4 7 400 0.1 32 4 1-dodecene 1000 110 450 9.4 7 425 0.1 31 5cyclohexane 1000 70 400 9.4 7 500 0.2 34 6 cyclohexane 1000 80 350 9.4 7500 0.1 39 7 cyclohexane 1000 100 350 9.4 7 300 0.2 48 8 1-dodecene 100080 350 9.4 7 500 0.1 36 9 1-dodecene 1000 90 450 9.4 7 450 0.1 33 101-dodecene 1000 100 450 9.4 7 550 0.1 26 11 1-dodecene 1000 90 350 9.4 7500 0.1 36 12 1-dodecene 1000 90 250 9.4 7 500 0.1 37 13 1-dodecene 100085 200 9.4 7 500 0.1 40 14 1-dodecene 1000 85 200 9.4 7 500 0.1 41

TABLE 3 Ethylene Oligomerization Performance Product Peak ProductivitiesTank Reactor kg Rx Solids, C₂H₄ Discharge C₂H₄ product/ kg Solids, wt. %to Solids, g STY, Carbon Number Purity conversion, K value, g ironproduct/ g/kg wax/wt. PE, solids/kg Lb/gal/ C₆, C₈, C₁₄, C₁₆, Examplewt. % (C₁₂/C₁₀) compound g Al prod. % PE wt. % Product hour wt. % wt. %wt. % wt. % 1 50.3 0.65 231 7.0 0.81 — — — 2.9 — — 96.1 95.7 2 67.2 0.60381 8.9 3.03 — — — 4.8 — — 88.3 84.8 3 75.6 0.62 370 10.3 4.89 — — — 5.2— — 83.6 82.8 4 31.8 0.64 237 6.6 1.31 — — — 3.5 — — 91.1 87.0 5 34.00.76 95 5.3 3.32 10.6/0.5  1.0 2238 1.7 — — 96.5 95.0 6 48.1 0.69 2095.8 1.86 6.3/0.2 0.9 12.0 3.1 — — 97.6 97.2 7 56.5 0.68 157 4.4 — 2.8/0.26 0.7 11.4 2.3 — — 97.5 97.1 8 74.2 0.69 473 13.2 3.78 15.1/0.400.9 26.0 7.1 99.1 98.1 93.0 91.2 9 72.2 0.65 412 11.5 3.81  1.9/0.15 0.529.8 6.2 98.9 97.8 91.1 89.0 10 70.7 0.55 387 10.8 10.8 — — — 5.8 98.598.5 92.5 87.6 11 65.3 0.64 447 12.4 0.87 10.1/0.54 1.1 19.7 6.7 99.398.4 93.5 91.0 12 79.9 0.66 451 12.5 6.21 15.2/0.94 2.4 38.1 6.7 98.396.7 89.5 85.2 13 77.5 0.67 430 12.0 8.58  8.6/0.48 0.9 18.0 6.4 99.298.4 94.3 93.6 14 78.8 0.66 439 12.2 1.72 17.3/1.41 1.9 32.2 6.6 98.897.5 94.2 93.6

DISCUSSION OF ETHYLENE OLIGOMERIZATION RESULTS

Ethylene oligomerizations Examples 1 and 2 were performed in cyclohexaneand 1-dodecene, respectively, utilizing([2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-t-butylphenylimine)methyl]-pyridine]FeCl₂).Since([2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-t-butylphenylimine)methyl]pyridine]FeCl₂)was not soluble in hydrocarbon solvent, dichloromethane was utilized asthe solvent for([2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-t-butylphenylimine)methyl]pyridine]FeCl₂).To test whether the metal complex could be prepared in-situ, and todetermine whether the ethylene oligomerization could be performed in theabsence of halogenated hydrocarbons, Examples 3 and 4 were performed incyclohexane and 1-dodecene, respectively, by preparing a solution of2-[(2,4,6-trimethylphenylimine)methyl]-6-[(3,5-dimethylphenylimine)methyl]pyridine)and Fe(acac)₃) in toluene. These examples show that ethyleneoligomerization can be performed with catalyst systems using a pyridinebisimine iron complex or an in-situ prepared pyridine bisimine ironcomplex and that both methods provide ethylene oligomerization catalystshaving comparable productivities. Comparison of Examples 1 and 2 showsthat ethylene oligomerization using 1-dodecene as an organic reactionmedium provided increased productivities but decreased 1-alkene purityin the C₁₄ and C₁₆ product fractions. Additionally, the use of1-dodecene reduced downstream fouling and aided in polymer handling.

Ethylene oligomerization Examples 5-7 and Examples 8-10 were performedusing cyclohexane and 1-dodecene, respectively, as the organic reactionmedium to determine the effect of temperature and organic reactionmedium on catalyst system productivities, polymer production, andproduct quality. Additionally, these Examples included a visualobservation of the autoclave reactor body and autoclave head to providea qualitative determination of the amount and type of polymer whichcollected in the autoclave reactor during the ethylene oligomerization.These qualitative results are tabulated in Table 4.

TABLE 4 Temp/Organic Example Reaction Medium Quantity Type 5 70°C./cyclohexane Heavy accumulation on reactor body Waxy and stringy withsome wall, reactor head surfaces, and stirrer strips wrapped aroundstirrer 6 80° C./cyclohexane Moderate accumulation on reactor body Waxyand stringy with some wall, reactor head surfaces, and stirrer stripswrapped around stirrer 7 100° C./cyclohexane Light accumulation onreactor body Stringy and wrapped around surface and reactor headsurface. stirrer Moderate stringy accumulation of stirrer 8 80°C./1-dodecene Light dusting on reactor body wall, Waxy/Dusty/Filmreactor head surfaces. Small amount of accumulation on stirrer 9 90°C./1-dodecene Thin film on reactor body wall, reactor Waxy/Dusty/Filmhead surfaces. Small amount of accumulation on stirrer 10 100°C./1-dodecene Light film on reactor body wall, reactor Waxy and slightlystringy head surfaces. Moderate accumulation on reactor head surfaces,and stirrer

Productivity data for the ethylene oligomerization in cyclohexaneindicate that there appears to be a sweet spot for productivity aroundan ethylene oligomerization temperature of 80° C. The cyclohexaneethylene oligomerization data also indicates that increasing theethylene oligomerization temperature can decrease product tank solidsand that low ethylene oligomerization temperatures can negatively impactolefin quality via a reduction in carbon number alkene purity.Qualitative observations of the solids remaining in the autoclavereactor indicate that increasing the ethylene oligomerization withcyclohexane as the organic reaction medium can decrease the amount ofsolid retained in the ethylene oligomerization reactor.

Productivity data for the ethylene oligomerization in 1-dodeceneindicate that increasing ethylene oligomerization data can cause aslight reduction in productivity and can decrease product tank solids.The 1-dodecene ethylene oligomerization data also indicates thatincreasing the ethylene oligomerization temperature can negativelyimpact olefin quality via a reduction in carbon number alkene purity.Qualitative observations of the solids remaining in the autoclavereactor indicate that increasing the ethylene oligomerization with1-dodecene as the organic reaction medium can increase the amount ofsolids retained in the ethylene oligomerization reactor.

Comparing the qualitative observations of the solids remaining in theautoclave reactor between the cyclohexane ethylene oligomerizations andthe 1-dodecene ethylene oligomerization runs, it appears using a highercarbon numbered hydrocarbon organic reaction medium can reduce theamount of solid remaining in the reactor. Additionally, it appears thatthe use of a higher carbon numbered hydrocarbon organic reaction mediumcan change the type of solid remaining in the reactor. In particular, itappears that using a higher carbon numbered organic reaction medium canchange the type of reactor solids from a waxy stringy solid than canquickly foul reactor operations to a dusty filmy solid which can be moreeasily flushed from the reactor during normal operation.

Examples 8-14 provide information regarding the impact that temperature,organic reaction medium (1-dodecene) to ethylene flow ratio can have onan ethylene oligomerization. The experiments show that 1) temperaturedoes not have a large impact on the K-vale at temperature ofapproximately 85° C. to 90° C., 2) space time yield can be maintained ahigh level at a temperature of approximately 85° C. to 90° C., and/or 3)increasing the organic reaction medium (1-dodecene) to ethylene flowrate can negatively impact the linear 1-alkene content of the C₁₄ andC₁₆ carbon number fractions.

Examples 13 and 14 show that the catalyst systems using the2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-methylphenylimine)methyl]pyridineligand and the2-[(2,4,6-trimethylphenylimine)methyl]-6-[(3,5-dimethylphenylimine)methyl]pyridine)ligand provide ethylene oligomerization that 1) can have similarproductivities, 2) can provide similar quantities of reactor and/ortotal product solids, and/or 3) can produce an oligomer product that canhave a similar linear 1-alkene content for the C₁₄ and C₁₆ carbon numberfractions.

What is claimed is:
 1. A process comprising: A) continuously introducing into a reaction zone i) ethylene, ii) an iron salt, iii) a pyridine bisimine, iv) an organoaluminum compound, and v) an organic reaction medium, and B) forming an oligomer product in the reaction zone, the reaction zone having i) an iron of the iron salt concentration in a range of 5×10⁻⁴ mmol/kg to 5×10⁻³ mmol/kg, ii) an aluminum of the organoaluminum compound to iron of the iron salt molar ratio in a range of 300:1 to 800:1, ii) an ethylene partial pressure in a range of 750 psig to 1200 psig, iv) an ethylene to organic reaction medium mass ratio in a range of 0.8 to 4.5, v) a temperature in a range of 75° C. to 95° C.; and optionally vi) a hydrogen partial pressure of at least 5 psi.
 2. The process of claim 1, wherein the organic reaction medium comprises one or more C₈ to C₁₈ aliphatic hydrocarbons.
 3. The process of claim 1, wherein the organic reaction medium comprises one or more C₈ to C₁₆ olefinic aliphatic hydrocarbons.
 4. The process of claim 2, wherein the organic reaction medium is substantially devoid of a halogenated compound.
 5. The process of claim 1, wherein the reaction zone has an aluminum of the organoaluminum compound concentration in the range of 0.75 mmol Al/kg to 2.6 mmol Al/kg, an aluminum of the organoaluminum compound to iron of the iron salt molar ratio in the range of 300:1 to 500:1, an ethylene partial pressure in the range of 750 to 1000 psi, and a temperature in the range of 80° C. to 90° C.; wherein the oligomer product formed in the reaction zone has a Schultz-Flory K value in the range of 0.4 to 0.9 and wherein the organic reaction medium consists essentially of one or more of C₈ to C₁₆ olefinic aliphatic hydrocarbons.
 6. The process of claim 5, wherein the organic reaction medium is selected from the group consisting of 1-decene, 1-dodecene, 1-tetradecene, or any combination thereof.
 7. The process of claim 1, wherein the pyridine bisimine comprises i) a 2,6-bis[(arylimine)hydrocarbyl]pyridine wherein the aryl groups can be the same or different, ii) a bis[(substituted arylimine)hydrocarbyl]pyridine, wherein the substituted aryl groups can be the same or different, or iii) an [(arylimine)hydrocarbyl],[(substituted arylimine)hydrocarbyl]pyridine.
 8. The process of claim 7, wherein 1) one, two, or three of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen independently are a halogen a primary carbon atom group or a secondary carbon atom group; and the remainder of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are hydrogen, 2) one of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen is a tertiary carbon atom group; none, one, or two of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen independently are a halogen, a primary carbon atom group or a secondary carbon atom group; and the remainder of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are hydrogen, 3) two of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen independently are a tertiary carbon atom group; none, or one of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen independently are a halogen, a primary carbon atom group, or a secondary carbon atom group; and the remainder of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are hydrogen, 4) one or two of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen independently are a tertiary carbon atom group(s); and the remainder of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are hydrogen, 5) one or two of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are a quaternary carbon atom group; and the remainder of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are hydrogen, or 6) all four of the substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are fluorine.
 9. The process of claim 6, wherein the pyridine bisimine is selected from the group consisting of 2,6-bis[(phenylimine) methyl]pyridine, 2,6-bis[(2-methylphenylimine)methyl]pyridine, 2,6-bis [(2-ethylphenylimine)methyl]pyridine, 2,6-bis [(2-isopropylphenylimine)methyl]pyridine, 2,6-bis[(2,4-dimethylphenylimine)methyl]pyridine, 2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-methylphenylimine)methyl]pyridine, 2-[(2,4,6-trimethylphenylimine)methyl]-6-[(3,5-dimethylphenylimine)methyl]pyridine, and 2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-t-butylphenylimine)methyl]pyridine and combinations thereof.
 10. A process comprising: A) continuously introducing into a reaction zone i) ethylene, ii) a pyridine bisimine iron salt complex, iii) an organoaluminum compound, and iv) an organic reaction medium; and B) forming an oligomer product in the reaction zone, the reaction zone having i) an iron of the pyridine bisimine iron salt complex concentration in a range of 5×10⁻⁴ mmol/kg to 5×10⁻³ mmol/kg, ii) an aluminum of the organoaluminum compound to iron of the pyridine bisimine iron salt complex molar ratio in a range of 300:1 to 800:1, iii) an ethylene partial pressure in a range of 750 psig to 1200 psig, iv) an ethylene to organic reaction medium mass ratio of 0.8 to 4.5, and v) an average temperature in a range of 75° C. to 95° C.; and optionally vi) a hydrogen partial pressure of at least 5 psi.
 11. The process of claim 10, wherein the organic reaction medium comprises one or more C₈ to C₁₈ aliphatic hydrocarbons.
 12. The process of claims 10, wherein the organic reaction medium comprises one or more C₈ to C₁₆ olefinic aliphatic hydrocarbons.
 13. The process of claim 11, wherein the organic reaction medium is substantially devoid of a halogenated compound.
 14. The process of claim 10, wherein the reaction zone has an aluminum of the organoaluminum compound concentration in the range of 0.75 mmol Al/kg to 2.6 mmol Al/kg, an aluminum of the organo aluminum compound to iron of the pyridine bisimine iron salt complex molar ratio in the range of 300:1 to 500:1, an ethylene partial pressure in the range of 750 to 1000 psi, a temperature in the range of 80° C. to 90° C.; wherein the oligomer product formed in the reaction zone has a Schultz-Flory K value in the range of 0.4 to 0.9; and wherein the organic reaction medium consists essentially of one or more C₈ to C₁₆ olefinic aliphatic hydrocarbons.
 15. The process of claim 14, wherein the organic reaction medium consists essentially of 1-decene, 1-dodecene, 1-tetradecene, or any combination thereof.
 16. The process of claim 10, wherein the pyridine bisimine or the pyridine bisimine of the pyridine bisimine iron salt complex comprises i) a 2,6-bis[(arylimine)hydrocarbyl]pyridine wherein the aryl groups can be the same or different, ii) a bis[(substituted arylimine)hydrocarbyl]pyridine, wherein the substituted aryl groups can be the same or different, or iii) an [(arylimine)hydrocarbyl], [(substituted arylimine)hydrocarbyl]pyridine.
 17. The process of claim 16, wherein 1) one, two, or three of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen independently are a halogen, a primary carbon atom group or a secondary carbon atom group; and the remainder of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are hydrogen, 2) one of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen is a tertiary carbon atom group' none, one, or two of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen independently are a halogen, a primary carbon atom group or a secondary carbon atom group; and the remainder of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are hydrogen, 3) two of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen independently are a tertiary carbon atom group; none, or one of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen independently are a halogen, a primary carbon atom group, or a secondary carbon atom group; and the remainder of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are hydrogen, 4) one or two of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen independently are a tertiary carbon atom group(s); and the remainder of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are hydrogen, 5) one or two of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are a quaternary carbon atom group; and the remainder of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are hydrogen, or 6) all four of the substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are fluorine.
 18. The process of claim 15, wherein the pyridine bisimine is selected from the group consisting of 2,6-bis[(phenylimine) methyl]pyridine, 2,6-bis[(2-methylphenylimine)methyl]pyridine, 2,6-bis [(2-ethylphenylimine)methyl]pyridine, 2,6-bis[(2-isopropylphenylimine)methyl]pyridine, 2,6-bis[(2,4-dimethylphenylimine)methyl]pyridine, 2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-methylphenylimine)methyl]pyridine, 2-[(2,4,6-trimethylphenylimine)methyl]-6-[(3,5 -dimethylphenylimine)methyl]pyridine, and 2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-t-butylphenylimine)methyl]pyridine.
 19. A process comprising: A) continuously introducing into a reaction zone i) ethylene, ii) an iron salt, iii) a pyridine bisimine, iv) an organoaluminum compound, and v) an organic reaction medium comprising one or more C₈ to C₁₈ aliphatic hydrocarbons; and B) forming an oligomer product in the reaction zone, the reaction zone having an average temperature in a range of 75° C. to 95° C.
 20. The process of claim 19, wherein the organic reaction medium comprises one or more C₈ to C₁₆ olefinic aliphatic hydrocarbons.
 21. The process of claim 20, wherein the organic reaction medium comprises 1-decene, 1-dodecene, 1-tetradecene, or any combination thereof.
 22. The process of claim 19, wherein the pyridine bisimine comprises i) a 2,6-bis[(arylimine)hydrocarbyl]pyridine wherein the aryl groups can be the same or different, ii) a bis[(substituted arylimine)hydrocarbyl]pyridine, wherein the substituted aryl groups can be the same or different, or iii) a [(arylimine)hydrocarbyl],[(substituted arylimine)hydrocarbyl]pyridine.
 23. A process comprising: A) continuously introducing into a reaction zone i) ethylene, ii) an pyridine bisimine iron salt complex, iii) an organoaluminum compound, and iv) an organic reaction medium comprising one or more C₈ to C₁₈ aliphatic hydrocarbons; and B) forming an oligomer product in the reaction zone, the reaction zone having an average temperature in a range of 75° C. to 95° C.
 24. The process of claims 23, wherein the organic reaction medium comprises one or more C₈ to C₁₆ olefinic aliphatic hydrocarbons.
 25. The process of claim 23, wherein the organic reaction medium comprises 1-decene, 1-dodecene, 1-tetradecene, or any combination thereof.
 26. The process of claim 23 wherein the pyridine bisimine comprises i) a 2,6-bis[(arylimine)hydrocarbyl]pyridine wherein the aryl groups can be the same or different, ii) a bis[(substituted arylimine)hydrocarbyl]pyridine, wherein the substituted aryl groups can be the same or different, or iii) a [(arylimine)hydrocarbyl],[(substituted arylimine)hydrocarbyl]pyridine. 